NO125592B - - Google Patents

Description

Cleaner for hard surfaces and

with bleaching and disinfecting properties.

The present invention relates to a cleaning agent' for hard surfaces and with bleaching and disinfecting properties, the new cleaning agent comprising, among other things, a stable compound which is a source of active chlorine as well as sulfamic acid or a water-soluble sulfamate, which under certain conditions of use improves the bleaching and cleaning effect of the cleaning agent when this is used to remove food stains, while at the same time the mixture is stable during storage.

The use of cleaning agents with bleaching and disinfecting properties

is well known. Certain spots such as however, tea stains are

difficult to remove even with effective bleaching compounds.

The use of sulfamic acid in hypochlorite bleaching agents for bleaching paper pulp is known and described in US Patent No. 3,177,111. Under the typical conditions prevailing during pulp bleaching, the sulfamic acid delays the bleaching action of hypochlorite.

The present invention thus relates to a cleaning agent mixture for hard surfaces and with bleaching and disinfecting properties, containing from 0 to 95 percent by weight of a finely divided water-insoluble abrasive, from 0 to 10 percent by weight of a water-soluble, anionic, non-ionic, zwitterionic or cationic organic detergent component , from 0 to 60 percent by weight of alkaline detergent builder, as well as sulfamate or sulfamic acid, as well as a stable compound capable of providing active chlorine in an amount of from 0.05 to 5 percent by weight of active chlorine.

The peculiarity of the cleaning agent mixture according to the invention

is that the mixture contains sufficient sulfamic acid or water-soluble sulfamate to give a ratio between active chlorine and sulfamic acid of from 500:1 to 1:1, the mixture having a pH under conditions of use of at least 10.5? and that the mixture optionally contains an inorganic or organic bromide in such an amount as to form from 1 to 150% bromide ion, based on the weight of total available chlorine, or a compound which provides available bromine in such an amount as to form from 0, 5 to 50 weight percent bromine, based on total available chlorine.

Other features of the invention appear from the patent claims.

Although it is known from the past that the combination of a hypochlorite bleach and sulfamic acid is a slower-acting,

less severe bleaching agent than hypochlorite alone when this is used for bleaching paper pulp, it has surprisingly been found that under the conditions that occur when using an alkaline cleaning agent, as described earlier, sulfamic acid increases the bleaching rate of cleaning agents when used on, for example, tea stains and ferric-tannat stains which are representative of food stains

containing tannic acid. High alkalinity and hypochlorite

Bleach will normally easily remove most stains. Certain spots such as however, ferritannat stains and tea stains are difficult to remove quickly. It is immediately understood that the faster a cleaning agent removes a stain, the more effective it will be for the housewife. The speed with which the cleaning agents according to the invention remove tannat stains and tea stains from dishes, laundry, etc., is increased by the presence of sulfamic acid or sulfamate.

Another stain type that is removed more quickly when sulfamic acid is present is "FD&C number <>>+ Red food coloring".

Suitable compounds which provide a source of active chlorine include chlorinated trisodium orthophosphate, trichlorocyanuric acid,

potassium and sodium dichlorocyanurate, 5?5-dimethyl-1,3-dichlorohydantoin, sodium and potassium benzenesulfonchloramines, sodium

and potassium para-toluenesulfonchloramines, sodium and potassium chlorobromocyanurates, 1-chloro-3-bromo-5,5-dimethylhydantoin, H-chlorosuccinimide, trichloro- and hexachloromelamines, and mixtures thereof . The preferred chlorine compound is chlorinated trisodium orthophosphate since it is relatively inexpensive and provides the necessary pH of at least 10.5-

Suitable inorganic bromides are water-soluble ones, especially alkali metal bromides such as sodium and potassium bromides. Suitable organic bromides include tetramethyl ammonium bromide, tetraethyl ammonium bromide, dimethyl coconut alkyl benzyl ammonium bromide, trimethyl dodecyl ammonium bromide and trimethyl benzyl ammonium bromide. Suitable compounds which provide active bromine include chloro-bromo-cyanurates, and hydantoins as mentioned above and the corresponding dibromo-cyanurates, bromo-succinimide, and dibromo-hydantoin. Other sources of active bromine include the bromomelamines and brominated trisodium orthophosphate. These bromides and sources of active bromine also increase the bleaching rates of the mixtures containing the active chlorine.

The amount of bromide ion is from 1 to about 150 percent by weight of the amount of active chlorine present, preferably from 25 to 135 percent by weight, and the amount of bromine may be from 0.5 to 50 percent by weight of the amount of active chlorine present,

preferably from 17 to 35 percent by weight. The beneficial effect of bromides in combination with hypochlorite bleaches is described in more detail in US Patent No. 2,815,311.

The sulfamic acid, or the water-insoluble sulfamate, is present in an amount sufficient to give a ratio of active chlorine to sulfamic acid (molar equivalents of sulfamate may be used instead of sulfamic acid) of from 500:1 to 1:1, preferably from 100:1

to 1.5:1, and even more preferably from 10:1 to 1.5:1, or from 6:1 to 3:1. An excess of sulfamic acid will likely damage the efficiency by reducing the speed of the bleaching and leading to a higher price of the product. A small drop in detergency will also be the consequence of using an excess of sulfamic acid as it undesirably lowers the pH of the mixture. The term "sulfamic acid" used herein also includes water-soluble sulfamates which give sulfamation in solution. Particularly preferred sulfamates include sodium and potassium sulfamates. Other water-soluble sulfamates include magnesium, calcium, lithium and aluminum sulfamates. Sulfamic acid is drawn four times as it is not particularly hygroscopic. Sodium and potassium sulfamates are also preferred. In a preferred embodiment, the sulfamates are dissolved in water and sprayed onto the abrasive as described below, and dried to give a mixture that is unexpectedly relatively unaffected by the hygroscopic properties of the sulfamates.

The sulfamic acid and the sulfamates are unique in that they lead to improved bleaching ability without adversely affecting the physical properties and other performance characteristics of the mixtures. Bromides can e.g. ok the bleaching speed, but they can affect

the smell of the mixture during use.

Sulfamic acid and sulfamates improve the odor stability of many perfume compounds used in cleaning and bleaching agents of the type referred to herein. In a preferred embodiment, the cleaning and bleaching agent contains from 0.01 to 1% by weight of perfume, and preferably from 0.1 to 0.3% by weight. The sulfamate stabilizes the perfume in the presence of active chlorine, especially when the perfume contains aldehydes, alcohols, esters and/or ketones. Protection for the aldehydes seems to last for a shorter time than for the alcohols,

the ketones or esters, but in all cases there is an improvement in perfume stability. This is very surprising when considered against the background that sulfamic acid and/or sulfamates improve the bleaching rate.

In a preferred embodiment of the cleaning agent mixture, a water-insoluble abrasive constitutes a major part of the mixture so that a scouring and cleaning agent is produced. The abrasive cleaners contain at least 60 percent by weight abrasive, preferably from 60 to 95 percent by weight. Almost any water-insoluble particulate abrasive may be used, and examples of water-insoluble abrasives suitable for use in the cleaners include finely divided particulate silicate abrasive such as quartz, silicon oxide, feldspar, pumice stone, zirconium silicate, volcanic ash, diatomaceous earth, kaolin, chalk, bentonite, talc and the like, calcium carbonate and aluminum oxide. A suitable particle size for this abrasive material is from 0.5 nm diameter to 0.001 mm diameter. Finer particles can also be used.

The amount of abrasive used is determined based on the final application. If the cleaning agent is to be used for washing dishes in an automatic dishwasher, there should preferably be no abrasive in the mixture.

The water-soluble organic detergent ingredients that can be used in the scouring and cleaning agent are anionic, non-ionic, zwitter-ionic and cationic organic ones. The preferred class of organic detergent ingredients is the anionic non-soap class. The preferred anionic ones are alkali metal alkylbenzene sulfonates wherein the alkyl group contains from about 10 to about 18 carbon atoms and alkyl sulfates containing from about 10 to about 18 carbon atoms and wherein the alkyl groups are preferably straight chain alkyl groups.

Examples of suitable detergent ingredients for use in the detergent mixture include that which is illustratively described in US Patent No. 3,318,817 in column <*>f, line 37 to column 6, line 30 and column 9, lines 6 to 57.

Suitable cationic detergent ingredients are those of the formula

R - N(R<2>),^ X^~\ in which R is an alkyl chain containing from

2

about 8 to about 20 carbon atoms, where R is selected from the group consisting of alkyl and alkanol groups containing from 1 to h carbon atoms and benzyl groups, normally not

more than one benzyl group and two R p groups can be united across either a carbon-carbon, ether, or imino bond to form a ring structure, and X represents a halogen atom, a sulfate-

group, nitrate group or another pseudohalogen group.

Specific examples are coconut alkyl trimethyl amine chloride, dodecyl dimethyl benzyl bromide and dodecyl methyl morpholine chloride.

The above-mentioned organic detergent ingredients are used in amounts not exceeding 10% by weight of the mixture and preferably in amounts of from 1 to 6% by weight of the mixture. The purpose of the organic detergent component is to provide the primary detergency effect in cooperation with the alkaline detergency builders described below. The lower limit is set by the washability requirements and the upper limit is set based on such considerations as clump formation, cleaning ability, foaming ability etc.

The alkaline washability builders normally provide the right one

pH of the mixture and improves the detergency effect of the organic detergent component. The alkaline detergency builder is used in amounts of less than 60 percent by weight of the mixture, preferably in amounts of from 3.5 to 15 percent by weight of the mixture. Suitable examples of alkaline washability builders include them

which is described in US Patent No. 3-309,319 in column h,

line kk to column 5? line 9. In the absence of alkaline detergency builders and if the compound producing active chlorine is not sufficiently alkaline, the pH must be adjusted to at least 10.5 with

addition of other alkaline materials such as e.g. alkali metal-. hydroxide.

In addition to the alkaline detergency builders, the mixtures may also contain up to approximately 5 percent by weight of the mixture of borax (sodium tetraborate decahydrate). Borax is preferably used together with chlorinated trisodium phosphate which. it stabilizes during storage.

The stabilization of the chlorinated trisodium phosphate also improves the odor of the mixtures.

Other ingredients may also be present in the compositions, and suitable inert inorganic salts may also be included in amounts less than about 20 percent by weight of the compositions. Examples of inert inorganic salts include sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, etc. Small amounts of other components can also be included, e.g. dirt-suspending agents such as e.g. sodium carboxy-methyl cellulose, sodium carboxy-methyl hydroxyethyl cellulose, optical brighteners, color pigments, antibacterial agents, oxidation inhibitors such as e.g. benzo-triazole, etc.

The invention can be better understood on the basis of the following specific Examples.

In examples I-V, the test procedure was as follows:

Hard plastic panels of the "Formica" type were cleaned" with silicon oxide abrasive and oxalic acid. The panels were then

covered with a concentrated tea solution, then with 0.1 M

FeSO^ • 7H2O, then with 0.1 M Na2C0^~and finally again with the concentrated tea solution. The panels were then dried, cleaned and rubbed. The procedure was repeated until a uniform soiling was achieved.

Rapid bleaching test: 25% slurries of the detergent samples in distilled water were prepared. These slurries were then poured over the soiled ones. panels as quickly as possible after production a? the slurries. The stained panels were bleached while placed in a rack which held the panels at an angle of 65° from the horizontal. Each bleach solution was poured over a portion of the soiled panel for a period of 5 seconds and the panel was then immediately cleaned and scrubbed dry. After the panel had been treated with all of the slurries on separate and defined sections of the panel, different parts of the panel were rated for whiteness on a scale of 1 to 10, with 10 representing absolute whiteness and 1 representing no stain removal, by three observers and the indicated grades are the average grades obtained for each of the tests.

EXAMPLE I.

EXAMPLE II.

In this example, varying amounts of sulfamic acid were added to Mixture 3 of Example I, replacing the abrasive.

The above figures demonstrate the importance of the ratio between sulfamic acid and active chlorine content.

EXAMPLE III.

In this example, different amounts of phosphoric acid (to adjust the pH) were added to the mixtures corresponding to mixture h in Example I. The mixtures 2, h, 6 and 8 also contained sulfamic acid.

This example shows that at a lower pH than about 10.5? e.g. pH 9 or 10, the sulfamic acid actually reduces the bleaching rate, but at pH values above about 10.5 the bleaching rate is slowed.

EXAMPLE IV.

0.183% sodium sulfamate was added to mixtures 3 and 1, respectively, of Example I, which were modified to contain 18.5% and 16.7% respectively of chlorinated trisodium orthophosphate. These mixtures

was then tested against the mixtures 3 °g in example I and the results were as follows:

EXAMPLE V.

The following detergent mixture is suitable for use in a dishwasher.

EXAMPLE VI.

The following test procedure was used in this example: Etched porcelain plates were soiled with a ferrotant solution and the stains were fixed with a sodium carbonate solution so that uniform stains were formed. 25% slurries of the detergent samples in distilled water were prepared and applied continuously over a local spot until the spot was removed, and the time required to remove the spot was recorded. The "mean bleaching time" is an average of four samples on four different spots. The less time allowed, the faster the bleaching occurs.

In the following samples (1-6) varying amounts were added

sulfamic acid to the base composition with 13.3% of the detergent mixture from Example I, 15.9% chlorinated TNF (0.52% active chlorine), 0.15% perfume, and the remainder was the quartz sand abrasive of Example I The pH values for 5% slurries of all these products were approximately 11.5.

In the following samples (7-12), varying amounts of sulfamic acid were added to the base composition with 13.3% of the detergent mixture from example I, 21.8% chlorinated TNF (0.71% active chlorine), 0.15% perfume, 3.0% borax and the rest the quartz-sand abrasive from example I.

The pH values for 5% slurries of all these products were approximately 11.2.

The sulfamic acid increases the rate of the bleaching with the highly chlorinated trisodium orthophosphate in the preceding mixture.

In the following samples (13-19), varying amounts of sodium sulfamate were added to the base composition with 13.3% of the detergent mixture from Example I, 15.75% chlorinated TNF (about 0.5% active chlorine), 0, 1 5% perfume, and the remainder was the quartz sand abrasive from Example I. The pH values for 5% slurries of all these products were approximately 11.5.

EXAMPLE VII.

When four separate mixtures of base composition with 13.3% of the detergent mixture from Example I, 15.75% chlorinated TNF (about 0.5% active chlorine) 0.15% sodium sulfamate, 0.15% of each of the following perfume mixtures, and the rest of the quartz-sand abrasive from Example I is prepared, the mixtures containing the perfume mixtures are stabilized with regard to the smell of the perfumes in comparison with similar mixtures containing no sodium sulfamate.

MIXTURE I.

MIXTURE II. MIXTURE III. MIXTURE IV.

The perfume mixture from mixture 3 is best stabilized by the sodium sulfamate and the perfume mixture from mixture 2 is stabilized by the sodium sulfamate to a remarkable degree in a somewhat shorter period of time. Mixture 1 is stabilized to a lesser extent and mixture h is stabilized the least by the sodium sulfamate. Sulfamic acid and other water-soluble sulfamates, e.g. potassium sulfamate when used on a molar basis instead of sodium sulfamate will also stabilize the perfume compositions in this example.

When in the preceding examples the following building components either fully or partially, e.g. in a ratio of 1:1, is used in place of the sodium tripolyphosphate, approximately equivalent results are obtained in that the sulfamic acid and/or sulfamates improve the bleaching rate of the mixtures as long as the pH of the mixture under the conditions of use is maintained above about 10.5, namely carbonates, tripolyphosphates , pyrophosphates, hexametaphosphates, ethylene-diamine-tetraacetates , N-(2-hydroxyethyl)-ethylene-diamine-triacetates, nitrile triacetates , N-(2-hydroxyethyl)-nitrilodiacetates , phytates , ethane-1-hydroxy-1,1-diphosphonates . the polymers have molecular weights of around 175,000 and mixtures thereof in e.g. the weight ratio 1:1, the cations in said building components being sodium or potassium cations.

When in the following examples the following abrasives are used in whole or in part, e.g. in a 1:1 weight ratio, instead of the silica abrasive, roughly equivalent results are achieved by the sulfamic acid and/or water-soluble sulfamates improving the bleaching rate of the mixtures: feldspar, pumice, zirconium silicate, volcanic ash, diatomaceous earth, kaolin , chalk, bentonite, talc, calcium carbonate and aluminum oxide, where the above-mentioned abrasives have the same particle size as the silicon oxide in the previous examples.

When, in the previous examples, the following detergent ingredients are used in whole or in part (e.g. in a 1:1 weight ratio) instead of sodium alkylbenzene sulphonate, roughly equivalent results are achieved in that the sulphamic acid and/or the water-soluble sulphamates improve the bleaching speed of the mixtures .

Sodium and/or potassium

(a) Coconut soap,

(b) Tallow soap,

(c) Alkyl sulphate in which the alkyl part writes

from coconut oil,

(d) Alkyl sulfate in which the alkyl radical

writes itself from tallow,

(e) Alkyl sulfonates prepared by sulfonation of alpha-olefins containing on average about 12 carbon atoms, (f) Alkyl benzene sulfonates containing straight-chain alkyl chains containing on average about 12 carbon atoms, (g) Alkyl glyceryl ether sulfonates in which the alkyl group

is written from coconut oil,

(h) Coconut fatty acid monoglyceride sulfates in which

the fatty acid group is written from coconut oil,

(i) Fatty acid monoglyceryl sulphonates in which the fatty acid group is derived from coconut oil,

(j) Alkyl-ethylene-oxide-sulphates in which the alkyl radical originates from tallow, and in which there are about 3

moles of ethylene oxide per moles of fatty alcohol,

(k) Alkyl-phenol-ethylene-oxide-sulphates containing approximately h units of ethylene oxide per molecule in which the alkyl radical contains approximately 9 carbon atoms, (1) Fatty acyl isethionates in which the fatty acyl groups are derived from coconut oil,

(m) The condensation product of ethylene oxide with a condensation product of propylene oxide and propylene glycol, the ethylene oxide constituting 50% of the total weight of the condensation product and the total molecular weight

of the condensation product is about 36OO.

(n) Alkyl-phenol-ethylene oxides in which the alkyl group contains approximately 12 carbon atoms and there are approximately 10 moles of ethylene oxide per mol.alkylphenol,

(o) Dodecyl dimethyl amine oxide,

(p) Tetradecyl-dimethyl-phosphine oxide,

(q) 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate,

(r) 3-(N,N-dimethyl-N-coco snot alkylammonio)-2-hydroxy-propane-1-sulfonate,

(s) 3-(N,N-diethyl-N-hexadecylammonio)-propane-1-carboxylate,

(t) Dodecyl-beta-alanine,

(u) N-dodecyl-taurine,

(v) N-dodecyl sparbt,

(w) Coconut alkyl triethylamine chloride,

(x) Dodecyl-dimethylbenzyl bromide,

(y) Dodecyl methyl morpholine methyl sulfate,

(z) Dodecyl-methyl-pyridine-nitrate, and

mixtures thereof, e.g. 1:1 mixtures of coconut soap and alkyl sulfonates', alkyl sulfates and alkyl benzene sulfonates j coconut oil fatty acid monoglyceride sulfates and fatty acyl isethionates<*>, and alkyl phenol ethylene -oxide and dodecyl-dimethyl-amine oxide.

When, in the preceding examples, the following sources of active chlorine are used in whole or in part (e.g. in a 1:1 weight ratio) instead of the chlorinated trisodium orthophosphate, roughly equivalent results are achieved in that the sulfamic acid and/or the sulfamates improve the bleaching rate of the mixtures : trichlorocyanuric acid, potassium and sodium dichlorocyanurates, 5,5-dimethyl-1,3-dichlorohydantoiri, sodium r and potassium benzenesulfonchloramines, sodium and potassium para-toluenesulfonchloramines, sodium and potassium chlorobromocyanurates , 1-chloro-3-bromo-5,5-dimethyl-hydantoin, N-chloro-succinimide, trichloro- and hexachloro-melamines, and mixtures thereof.

When, in the preceding examples, the following compounds are used in whole or in part (e.g. in a 1:1 weight ratio) instead of the sulfamic acid and/or the sodium sulfamate, approximately equivalent results are obtained by improving the bleaching speed of the mixtures: potassium sulfamate , lithium sulfamate, magnesium sulfamate, calcium sulfamate, and aluminum sulfamate.

When, in the foregoing examples, one of the following additional ingredients is added in an amount to give an amount of bromine equal to about 35 percent by weight of the active chlorine or an amount of bromide ion equal to about 67 percent by weight of the active chlorine, approximately equivalent results are obtained in that the sulfamic acid and/or the water-insoluble sulfamates improve the bleaching rate of the mixtures: sodium bromide, potassium bromide, tetramethylammonium bromide, tetraethylammonium bromide, dimethyl-coconut-alkyl-benzyl-ammonium bromide, trimethyl-dodecyl-ammonium bromide , trimethyl-benzyl-ammonium bromide, sodium and potassium dibromocyanurates, bromo-succinimide, dibromo-hydantoin, tetrabromomelamine and brominated trisodium orthophosphate.

All of the aforementioned mixtures can be used to bleach tea stains

by forming aqueous slurries or looseners containing from 1 to 50% of the mixtures so that an aqueous bleaching agent containing from 0.06 to 0.3% by weight of active chlorine is produced and that this aqueous bleaching agent is applied to the tea stains.

It is surprising that sulfamic acid and/or water-soluble sulfamate will improve the bleaching rate of this type of compositions without adversely affecting the stability of the compositions. It is also surprising that it is only in alkaline media, which are buffered to pH below about 10.5, that sulfamic acid and/or water-insoluble sulfamate improves the bleaching rate of the compositions. It is also surprising that the mixtures can be used so effectively against tea stains, when similar bleaching mixtures, without the sulfamic acid or sulfamate present, are less effective.

Claims (3)

1. Detergent mixture for hard surfaces and with bleaching and disinfecting properties, containing from 0 to 95 percent by weight of a finely divided water-insoluble abrasive, from 0 to 10 percent by weight of a water-soluble, anionic, nonionic, zwitterionic or cationic organic detergent component, from 0 to 60% by weight alkaline detergent builder, as well as sulfamate or sulfamic acid, as well as a stable compound capable of providing active chlorine in an amount of from 0.05 to 5% active chlorine by weight, characterized in that the mixture contains sufficient sulfamic acid or water-soluble sulfamate to to give a ratio between active chlorine and sulfamic acid of from 500:1 to 1 m, the mixture having a pH under conditions of use of at least 10.5, and that the mixture optionally contains an inorganic or organic bromide in such an amount that it is formed from 1 to 150% bromide ion, based on the weight of total available chlorine, or a compound which provides available bromine in such an amount that it then nnes from 0.5 to 50 weight percent bromine, based on total available chlorine. 2. Cleaning agent as specified in claim 1, characterized in that the source of active chlorine consists of chlorinated trisodium orthophosphate. 3. Cleaning agent as specified in claim 1, characterized in that the ratio between active chlorine and sulfamic acid is from 10:1 to 1.5:1.