NO125453B - - Google Patents

Description

Detergent.

The invention relates to detergents containing a proteolytic enzyme and an organic surface-active agent to improve the washing effect, as well as possibly sodium perborate.

Enzymes have been used in detergents because they are special

effective against various common stains attached to textile materials and laundry. In particular, proteolytic enzymes, which are capable of digesting and breaking down proteinaceous matter, are effective in removing proteinaceous stains, such as blood, transpiration, milk, cocoa, milk and other sauces ete.., from textiles and laundry This digestion or breakdown of proteinaceous matter facilitates the removal of dirt with the detergent.

According to the invention, the detergent is added with 1-10% by weight of a hydroxylamine compound or hydrazine compound with at least one free hydrogen atom in the hydroxylamine nucleus or the hydrazine nucleus.

It has been shown that the presence of the hydroxylamine compound or the hydrazine compound increases the effect of the enzyme-containing detergent both during exposure and washing.

The surface-active agent which can be used can be any commonly used compound with surface-active or detergent properties. The most preferred are water-soluble surface-active compounds with anionic or non-ionic properties. The anionic surface-active compounds include the surface-active compounds or detergent compounds containing an organic hydrophobic group and an anionic solubilizing group. As typical examples of anionic dissolving groups, sulphonate, sulphate, carboxylate and phosphate can be mentioned. As examples of suitable anionic surfactants that can be used according to the invention, mention can be made of the soaps, such as the water-soluble salts of higher fatty acids or rosin acids, which can be derived from fats, oils and waxes of animal, vegetable or marine origin, e.g. the sodium soaps of tallow, fat, coconut oil, tallow oil and mixtures thereof, and the sulfated and sulfonated synthetic surface-active compounds, especially those with 8-26, preferably 12-22, carbon atoms per molecule.

Examples of suitable synthetic anionic surface-active compounds can be mentioned the mononuclear higher alkyl-aromatic sulfonates, such as the higher alkylbenzene sulfonates containing 10 - 16 carbon atoms in the alkyl group in a straight or branched chain, e.g. the sodium salts of decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl or hexadecylbenzenesulfonate and the higher alkyltoluene, rxylene and phenolsulfonates, alkyl naphthalene sulfonate, ammonium diamyl naphthalene sulfonate and sodium dinonyl naphthalene sulfonate, sulfated aliphatic alcohols, such as sodium lauryl and hexadecyl sulfates, triethanolamine lauryl sulfate and sodium oleyl sulfate, sulfated alcohol ethers, such as lauryl, tridecyl

or tetradecyl sulfates comprising 2-h ethylene oxide groups, sulfated and sulfonated fatty oils, acids or esters, such as the sodium salts of sulfonated castor oil and sulfated rhododendron oil, sulfated hydroxyamides, such as sulfated hydroxyethyllauramide,

sodium salt of lauryl sulphoacetate, sodium salt of dioctyl sulphosuccinate and sodium saltate of oleylmethyl tauride.

Other anionic surfactants which can be used according to the invention^ include olefin sulphonates typically containing 8 - 25 carbon atoms*; It is also aimed according to the invention to use sulfuric acid esters of polyhydric alcohols which are incompletely esterified with higher fatty acids, e.g. coconut oil monoglyceride monosulfate and tallow diglyceride monosulfate, and the hydroxysulfonated higher fatty acid esters, such as the higher fatty acid esters of low molecular weight alkylolsulfonic acids, e.g. oleic ester of isethionic acid. The non-ionic surface-active agents are surface-active compounds or compounds with detergent properties which contain an • organic hydrophobic group and a hydrophilic group which is a reaction product of a dissolving group, such as carboxylate, hydroxyl, amide or amino, with ethylene oxide or with polyethylene glycol which is the polyhydration product thereof. Examples of non-ionic surfactants include the condensation products of alkylphenols with ethylene oxide, e.g. the reaction product of isooctylphenol with 6-30 ethylene oxide units, condensation products of alkylthiophenols with 10 - .15 ethylene oxide units, condensation products of higher fatty alcohols, such as tridecyl alcohol with ethylene oxide, ethylene oxide addition products of monoesters of hexavalent alcohols and internal ethers thereof, such as sorbitan monolaurate, soTbitol monooleate and mannitan monopalmitate, and the condensation products of polypropylene glycol with ethylene oxide. Cationic surfactants can also be used. These are detergent-wetting surface-active compounds containing an organic hydrophobic group and a cation-active solubilizing group. Amine and quaternary groups are typical chilon-active solubilizing groups. Examples of suitable synthetic cationic surfactants include diamines, such as the diamines with the formula RNHC2H^NH2 where R is an alkyl group with 12 - 22 carbon atoms, such as N-aminoethylstearylamine and N-aminoethylmyristylamine, amide-bonded amines, such as amines with the formula RVCONHCgH^ NHg, where R' is an alkyl group with 12-18 carbon atoms, such as N-aminoethylstearylamide and N-aminoethylmyristylamide, quaternary ammonium compounds where typically one of the groups bound to the nitrogen atom is an alkyl group with approx. 12 - 18 carbon atoms and three of the groups bound to the nitrogen atom are alkyl groups containing 1-3 carbon atoms, including alkyl groups with 1-3 carbon atoms and with inert substituents, such as phenyl groups, and where an anion is present, such as halogen, aceta. t, methosulfate etc. As examples of typical surface-active quaternary ammonium compounds can be mentioned ethyldimethylstearylammonium chloride, benzyldimethylstearylammonium chloride, trimethylstearylammonium chloride, trimethylcetylammonium bromide, methylethyldilaurylammonium chloride, dimethylpropylmyristylammonium chloride and the corresponding methosulfates and acetates. The surface-active compounds used according to the most preferred aspects of the invention are those which have anion-active properties. The most preferred water-soluble anionic surface-active compounds are the ammonium salts and substituted ammonium salts, such as mono-, di- and triethanolamine, alkali metal salts, such as sodium salts and potassium salts, and alkaline earth metal salts, such as calcium salts and magnesium salts, of the higher alkylbenzene sulfonates, the higher alky.1 sulfates and the higher fatty acid mcnoglyceride sulfates. The particular salt will be chosen depending on the particular mixture and the relative amounts therein. The surface-active agent is usually used in an amount of 5-95% by weight of the surfactant, preferably 10-25% by weight. The proteolytic enzymes used according to the invention act on proteinaceous material and catalyze in a hydrolysis reaction the digestion or breakdown of such material when it is present as stains on linen or woven fabrics. The enzymes work within a pH range of 4 - 12, which generally occurs during washing. They can also be effective even at moderately high temperatures as long as they are not broken down by these. Certain proteolytic enzymes are active at a temperature of up to 80°G and above. They are also active at room temperature and down to 10°C. As particular examples of proteolytic enzymes that can be used according to the invention, pepsin, trypsin, chymotrypsin, papain, bromelain, colleginase, keratinase, carboxylase, aminopeptidase, elastase, subtilisin and aspergillopepidase A and B can be mentioned. It is preferred to use subtilisin enzymes prepared and cultivated from special strains of spore-forming bacteria, especially Bacillus subtilis. Metalloproteases which contain divalent ions, such as calcium, magnesium or zinc, bound to their protein chains, can also be used. ;The enzyme preparations are generally very finely divided, and often practically incompressible powders. The particle diameter in a typical powdered enzyme preparation is substantially below 0.15 mm and generally above 0.01 mm, e.g. ea. 0.1 mm. Up to 75% of the material may e.g. have a particle diameter of 0.149 film or less. On the other hand, the blow-dried grains usually have a much larger particle size, as the majority of the grains have a diameter of at least approx. 0.2 mm, e.g. about. 0.3 or 0,, A . rm or even 0.5, 1 or 2 mm. The enzyme preparations are diluted, as a rule, with salts, such as calcium sulphate, and inert tea. materials. They are chemically stable typically at a pH of 5 - 10, and at an alkaline pH of 8.5 - 9; they withstand temperatures of 4:9 - 77° C. with relatively little cleavage and in a time of from .2 hours at high temperatures to over 1 day at lower temperatures. The different proteolytic enzymes have different degrees of effectiveness in terms of facilitating the removal of stains from textiles and linen The enzyme is preferably present in powder form and is mixed into the detergent. It is usually used in an amount of 0.01 - 4% by weight of the detergent, preferably 0.05 - 1% by weight, e.g. 0 - 0.5 percent by weight; In addition to the above-mentioned materials, the detergent according to the invention can also contain an 'additive salt or building salt for the surface-active compound..' The additive can be any of the commonly known ., water-soluble, inorganic building salts. or it "may be -a vtmnop.plnsel lg, organic ex illelses.raid.d-el, such as natr-iumni.tr.Lltrioeetr-t,., or mixtures thereof- .. * -De. water-soluble, inorganic building salts, such as an alkali metal, alkaline earth metal or heavy metal salt or mixtures thereof. An ammonium, or an ethanioammonium salt can also be added in a suitable amount, but it is generally preferred to

use sodium and potassium salts. Examples include the water-soluble sodium and potassium phosphates, silicates, carbonates, bicarbonates, borcites, sulfates and chlorides.

alkaline building salts, such as polyphosphates, silicates and borates, are particularly preferred.

In the mixtures of water-soluble, inorganic building salt used in the detergents, it is often preferred to use a mixture of sodium tripolyphosphate and sodium or potassium bicarbonate, as a combination or mixture of salts where the ratio between bicarbonate and tripolyphosphate is 1:1 - 3:1.

Sodium tripolyphosphate of both phase I and phase II and mixtures thereof can be advantageously used in the detergents. The common, commercially available tripolyphosphate consists essentially of the phase II material. The commercially available polyphosphate material is, as a rule, essentially tripolyphosphate, e.g. 87 - 95%, with smaller amounts, e.g. 4 - 13%, of other phosphates, e.g. pyrophosphate and orthophosphate. Hydrated sodium tripolyphosphate can also be used. Trisodium orthophosphate can be used in the indicated amounts.

Sodium or potassium bicarbonate is an effective pH buffer.

Bicarbonate t; can be used directly as anhydrous bicarbonate or as sesquicarbonate, which is a hydrate containing both bicarbonate and carbonate.

Other suitable building salts that can be used include the water-soluble sodium and potassium silicates, carbonates,

-borates, -chlorides and -sulfates.

If a building salt is used, it is preferable

present in an amount of 50 - 90 percent by weight of the detergent.

The detergent may also contain additives, such as sodium carboxymethylcellulose or polyvinylpyrrolidone. These additives can be present in an amount of 0.1 - 5% by weight of the detergent. This may also contain smaller quantities

optic white matter. perfumes and preservatives. A per-oxygen compound can also be used, such as sodium perborate in an amount of e.g. 3 - 35% of the detergent. If a peroxygen compound is used, it is best to use larger amounts of the hydroxylamine compound or the hydrazine compound.

The hydroxylamine compound or the hydrazine compound can be added as such or as a salt, e.g. such as hydrochlorides, sulfates, nitrates, phosphates, fluorosilicates, formates or oxalates. Hydroxylamine, hydrazine, phenylhydrazine, carbamoylhydrazine and N-phenyl-N'-carbamoylhydrazine are examples of suitable compounds. If substituted hydroxylamine or hydrazine compounds are used, these must have at least one unsubstituted hydrogen in the hydroxylamine or hydrazine nucleus. Mono-, di- or tri-substituted hydrazine can thus be used. The substituent or substituents may be alkyl, e.g. methyl or butyl, or aryl, e.g. phenyl, or other types, e.g. carbamyl.

In the examples and in the description, all percentages are based on weight if nothing else is stated.

Example 1

This example shows the effect of adding hydroxylamine hydrogen chloride to an enzyme-containing detergent both during blotting and washing.

A. The exposure resolution was a resolution. in water of (a) a commercially available built-up synthetic detergent detailed below, at a concentration of 5 g/litre, (b) a commercially available proteolytic enzyme agent, "Alcalase", at a concentration of 0.05 " g/liter, and (c) sodium perborate at a concentration of 0.005 molar. Where indicated, hydroxylamine hydrogen chloride was also used. Standard samples of soiled cotton fabrics with strong, colored stains of proteinaceous material, such as blood, transpiration, milk, cocoa, sjy and the like, with earbon black pigment, were exposed for 60 minutes in the exposure solution at room temperature.10 g soiled toy per liter of exposure solution was used.

After exposure for 60 minutes, the toy samples were removed from the solution and then rinsed. The clothes' reflectance was then measured. An increase in the reflection obviously indicates an improved purity of the test pieces.

The following table reproduces the improvement achieved by using hydroxylamine hydrogen chloride:

B. For washing, the previously exposed toy was immersed in a freshly prepared solution with the same composition as that used for the exposure, and washed with periodic agitation for 30 minutes at approx. 100°C. 10 g of exposed, soiled toy was used per liters of detergent.

The following table shows the improvement achieved by using different amounts of hydroxylamine hydrogen chloride in the solution:

Example 2

In this example, an enzyme-containing exposure solution was with the same composition as in Example 1 A, used, except that it did not contain perborate. The exposure conditions were the same as in Example IA.

The following table reproduces the improved reflection obtained by using different amounts of hydroxylamine hydrogen chloride in the reading:

Example 3

Example 1 was repeated using hydrazine sulfate instead of hydroxylamine hydrochloride. -The following results were achieved:

The commercially available detergent used in examples 1 - 4 had the following composition?

The proteolytic enzyme, "Alcalase", which was used in examples 1 - 4, is distinctive in that it has its greatest proteolytic activity at a pH of 8 - 9• This activity measured for it from Novo Industri A/S, Copenhagen, Denmark commercially available enzymes include 1.5 Anson units per gram of enzyme. The commercially available enzyme is a crude extract of bacillus subtilis culture and contains approx. 6% pure, crystalline, proteolytic material.

Example 4

In this example, soiled toys with proteinaceous stains were soaked for 60 minutes at room temperature in a solution containing 0.05 µl of "Alcalase", 0.0062 ml of sodium perborate per liter and 5 g per liter of the commercially available detergent in water together with 0.002 mol per liters of one of the compounds listed in the following table. The exposed toy was then washed for 30 minutes at 95 - 100 C with periodic stirring in a freshly prepared solution with the same composition as the exposure solution.

The results are expressed by (a) the turbidity of the blobbing solution used, (b) the turbidity of the washing solution used and (ab) the sum of these two turbidities. An increase in the turbidity of the solution has been shown to suggest that a greater amount of the dirt has been transferred from the toy to the solution during use.

When carrying out the turbidity tests, the proteins in the liquid were first precipitated by adding sulfuric acid, and the optical density of the protein dispersion formed was measured using light with a wavelength of 405 mvi.

Two types of soiled toys were used. One was

had been soiled with chocolate, and the other, which in the following table is denoted by "biosoil", was the same as that used in example 1.

As is known, sodium perborate is commercially available in two different forms, i.e. as the monohydrate and the tetrahydrate. Both of these forms can be used according to the invention. In the above examples, sodium perborate tetrahydrate was used, but excellent results are also obtained by using the monohydrate.

Claims (1)

Detergent containing - an organic surface-active agent and a proteolytic enzyme, as well as possibly sodium perborate, characterized in that - there is also added 1-1 G weight# of a hydroxylamine compound or hydrazine compound with - at least one free hydrogen atom in the hydroxylamine core or the hydrazine core.