SE431558B - Aqueous, Enzymatic, Liquid Detergent Composition - Google Patents

Description

In this Japanese patent application, these polyalcohols, for example sorbitol and glycerol, are used in an amount of at least 5% by weight of the finished composition and preferably 10-30% by weight. Borax is used in an amount of at least 20% and preferably 50 - 100 weight. The weight ratio of polyalcohol: borax in the composition should therefore be equal to or greater than 1 percent of the amount of polyalcohol.

In addition, compositions of this prior proposal have a pH in the range of 3.9 to 7.4, as experimentally shown by a repetition of Example 1.

It has been found according to the invention that the storage stability of enzymatic liquid detergent compositions having a pH of above 7.5 and preferably between 8.5 and 11.0 (at 25 ° C) can be significantly improved by incorporating into them a stabilizing systems comprising one or more polyhydroxy compounds, defined in more detail below, and boric acid or a boron equivalent thereof, wherein the weight ratio of polyhydroxy compounds: boric acid or equivalent to boric acid is less than 1 (calculated on the basis of borax). In comparison with combinations according to the aforementioned Japanese patent application, systems according to the invention show significantly improved enzyme stabilizing effect.

The polyhydroxy compounds used in the present invention contain only C, H and O atoms. They are free of other (functional) substituting atoms, for example N-, S- and similar atoms. The polyhydroxy compounds should contain at least 2 hydroxy groups and may contain up to 6 hydroxy groups. Typical examples of polyhydroxy compounds which are particularly suitable for use according to the invention are diols, for example 1,2-propanediol, ethylene glycol, erythriton, polyols, for example glycerol, sorbitol and mannitol. I I In general, the polyhydroxy compound is present in an amount of at least 4% by weight of the finished composition and up to 25% by weight thereof. Preferably, the amount varies from 5 to 15% by weight of the finished composition.

The boric acid or its boron equivalent, for example boron oxide, borax and other alkali metal borates which can react with a polyhydroxy compound, for example sodium, ortho-, -meta- and -pyro- borates, are used in such an amount that the weight ratio of polyhydroxy compound: boron compound is less than 1 (calculated on the basis of borax).

This means that the boron compound is used in an amount of more than 100% of the amount of polyhydroxy compound. In general, the amount varies from> 100 to 200% by weight and preferably from> 100 to 160% by weight of the polyhydroxy compound.

The weight ratio of polyhydroxy compound: boric acid or equivalent thereof is less than 1 and generally from 0.5 up to immediately below 1.

The enzymatic liquid compositions in which the stabilizing systems of the invention are incorporated may be aqueous liquid systems, for example simple solutions, but are preferably aqueous liquid detergent compositions containing, as essential constituents enzymes, active detergents and water, the pH value being is above 7.5 and preferably between 8.5 and 11.0 or adjusted to these values by appropriate means.

The enzymes to be incorporated are proteolytic, amylolytic and cellulolytic enzymes as well as mixtures thereof. They may be of any suitable origin, for example vegetable, animal, bacterial, fungal and yeast origin. However, the choice is governed by a number of factors, for example the pH activity and / or stability optimum, thermostability, stability in relation to active detergents, builders, etc. In this regard, bacterial or fungal enzymes, such as bacterial amylases and proteases, as well as fungal cellulases are preferred.

The invention is particularly suitable for enzymatic, liquid detergents containing bacterial proteases, for which pH optima are in the range between 8.0 and 11.0, but also enzymes with slightly lower or higher pH optimum can be used in compositions according to the invention using of the benefits of this.

Suitable examples of proteases are subtilisins obtained from certain strains of B. subtilis and B. licheniformis, for example commercially available subtilisins Maxataseqæ (from Gist--Brocades NV, Delft, Holland) and Alcalasea (from Novo Industri A / S, Copenhagen, Denmark ).

As stated above, the invention is particularly advantageous for enzymatic, liquid detergents containing enzymes with pH activity and / or stability optima at or above 8.0, for example enzymes which are also commonly referred to as highly alkaline enzymes.

Particularly suitable is a protease obtained from a strain of Bacillus with maximum activity in the pH range 8 - 12, which has been developed and sold by Novo Industri A / S under the registered trademark Esperaseqa. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 to Novo. High alkaline amylases and cellulases can also be used, for example α-amylases obtained from a particular strain of B. licheniformis, which are described in more detail in British Patent Specification 1,296,839 (Novo).

The amount of enzymes contained in the liquid composition may vary from 0.001 to 10% by weight and preferably from 0.01 to 5% by weight.

The liquid detergent compositions of the invention further comprise as an essential ingredient an active detergent material, which may be alkali metal or alkanolamine soap of a C10-C24 fatty acid, including polymerized fatty acids or anionic, nonionic, alkationic, zwitterionic or amphoteric, of such materials.

Examples of anionic synthetic detergents are salts (including sodium, potassium, ammonium and substituted ammonium salts, for example mono-, di- and triethanolamine salts) of C9-C23-alkylbenzenesulfonates, C8-C22 primary or secondary alkanesul phonates, C8-C24-olefin sulphonates, sulphonated polycarboxylic acids, produced by sulphenation of the pyrolysis product of alkaline earth metal citrates, for example as described in British Pat. to 10 moles of ethylene oxide), and further examples are described in "Surface Active Agents and Detergents" (Vol. I and II). by Schwartz, Perry and Berch.

Examples of nonionic synthetic detergents are condensation products of ethylene oxide, propylene oxide and / or butylene oxide with C8-C18-alkylphenols, CB-C18 primary or secondary aliphatic alcohols, C8-C18 fatty acid amides, further examples of nonionic detergent aminoids include tertiary with a C 8 -C 18 alkyl chain and two C 1-3 alkyl chains. The publications cited above also describe further examples of nonionic detergents.

The average number of moles of ethylene oxide and / or propylene oxide contained in the aforementioned nonionic detergents ranges from 1 to 30 and mixtures of different nonionic detergents, including mixtures of nonionic detergents with lower and higher degree of alkoxylation. can also be used.

Examples of cationic detergents are quaternary ammonium compounds, for example alkyldimethylammonium halides, but such cationic substances are less preferred for incorporation into enzymatic detergent compositions. Examples of amphoteric or zwitterionic detergents are N-alkylamino acids, sulfobetaines, fatty acids and condensate at the relatively high cost, these are usually used in combination with an anionic or nonionic detergent. Mixtures of the different types of active detergents may also be used and mixtures of an anionic and a nonionic detergent active compound are preferred. Soaps (in the form of sodium, potassium and substituted ammonium salts, for example triethanolamine salts) of C10-C24 fatty acids, as well as of polymerized fatty acids, can also be used, preferably in combination with an anionic and / or nonionic synthetic detergent, and can exert a beneficial effect on the foaming properties of the finished composition.

The amount of the active detergent material varies from 10% to 60%. If mixtures of, for example, anionic and nonionic detergents are used, the relative weight ratio varies from 1: 1 to 1:10. If a soap is also incorporated, the amount thereof is from 1 to 40% by weight. Although the liquids may contain up to 40% of a suitable builder, for example sodium, potassium and ammonium or substituted ammonium pyro- and tripolyphosphates, nitrilotriacetates, ether polycarboxylates, citrates, carbonates, orthophosphates, polyvinyl molytes, for example maleic anhydride copolymers, etc., the present invention is particularly advantageous for use in liquid detergents lacking builders.

The amount of water contained in the detergent compositions of the invention varies from 5 to 70% by weight.

Other conventional materials may also be included in the liquid detergent compositions of the invention, for example, soil suspending agents, hydrotropic agents, corrosion inhibitors, dyes, perfumes, silicates, optical brighteners, defoamers, antifoams, microbicides, germicides, discolorants, discolorants opacifiers, fabric softeners, oxygen-releasing bleaches, for example sodium perborate or percarbonate with or without bleach precursors, buffering agents and the like. The pH of the finished composition is higher than 7.5 and should preferably be in the range 8.5 to 11.0 and buffered if required to a value within this range by the addition of a suitable buffer system (for example with dimethylglycine).

The invention is illustrated in more detail below with exemplary embodiments. In the exemplary embodiments, the amounts are given as a percentage by weight. According to the examples, the magnitude of the half-life of the enzyme was determined as follows: A continuously sampled sample from a solution to be tested was continuously diluted (1: 200) and tested continuously for enzymatic activity (for proteolytic activity, casein was used as substrate). The logarithm of the remaining activity was plotted against time and the velocity constant K1 of the first order was calculated. The enzyme half-life time extension Ft is defined as follows: Kl (without stabilization system) ty / 2 (with stabilization system) Ft = = Kl (with stabilization system) ty / 2 (without stabilization system ty / 2 = time period within which it the enzymatic activity y is half of the original enzymatic activity.

Example 1

According to this example, aqueous systems containing a bacterial protease, Alcalasea from Novo, were tested. These aqueous systems contained per liter: 0.2 mol / liter pentasodium tripolyphosphate 0.12 mol / liter dimethylglycine "1.7 g Alkalase® (activity 10.6 AU / q). The pH of the solution was 10 and the temperature 57 ° C The rate at which activity loss of the enzyme occurred was measured in this system with and without the stabilization system as indicated below and the half-life elongation factor of the enzyme was determined.The following results were obtained.?7í2284-4 7 Stabilization system (viïâgggcent) ï: ââ: No. Polyhydroxy- P Ft: compound (P) Borax (B) PB É -Value 1 ethyl18ng1ykO1 + 10 15.4 0.649 16.7 2 "+ 6 9.2 0.662 8.3 3" »_ 10 - - 1 .9 4 glycerol + 10 10.3 0.970 14.7 "_ - io - - 1.8 6 1,2-propanediol + 6 7.5 0.8 6.7 7 sorbitol + 10 10.5 0.952 3.9 8 "+ 10 5.2 1.923 2.6 9" _ 10 - - 1.7 mannitol + 10 10.5 0.952 3.2 11 "w + 10 5.2 1.923 2.3 12" - - 1o - - 1 These results show the increasing Ft values obtained with the stabilization systems according to the invention. Experiments Nos. 8 and 11 do not comply with the invention (å ratio> 1) and show that with these conditions significantly reduced Ft values are obtained, compared with å ratios <1. Experiments no. 7 - 9 and 10 - 12 show that a reduced river ratio gives better Ft values, in contrast to the prior art which states that the river ratio should be eel. With 2, 4, 8 and 9.45% borax alone (no polyhydroxy compound added) the following Ft values were obtained: 1.0, 1.3, 1.8 resp. 2.4.

Example 2.

This series of experiments used a bacterial protease "Esperase" G9 from Novo (activity 41.5 KNPU / Q) - The water systems were identical to those of Example 1 but the temperature in this experiment was eo ° c. with 4% erythritan and 7.4% borax (å = 0.54), Ft = 2.5 was obtained.

Example 3.

In a manner analogous to Example 1, systems were tested with a bacterial Q-amylase (Thermamyl G9). The water systems contained per liter: 8 0.12 M pentasodium tripolyphosphate 0.1 M glycine 0.5 g Thermamylê (activity 450 KNU / 9). The pH was 9.95 and the temperature 59.3 ° C. With a stabilization system containing 6% ethylene glycol + 9.2% borax (š ~ with a ratio of 0.65), an Ft value of 2.2 was obtained.

Exemgel 4.

Example 1 was repeated with a stabilization system containing 10% glycerol and varying amounts of borax. The following results were obtained: Glycerol Borax (%) P / B ratio Ft a) 10% in all '14 0.71 ll, 6 trials _ _ b) _12 0.83 12.8 C) '11 0.91 14, 1 ä) 10.6 0.94 14.2 e) 10.35 0.97 14.7 f) 10 1.0 10.0 g) 8 1.25> 6.8 h) 6.25 1.6 4.7 i) U 5 2 3.4 j) 22.5 4 2.3 k) O - 1.8

Claims (8)

7712284-4 Patent claims. Aqueous, enzymatic, liquid detergent composition with improved storage stability, characterized in that the composition comprises a stabilization system comprising a) 4 to 25% by weight, based on the finished composition, of one or more polyhydroxy compounds containing only C- , H * and O atoms, and containing 2 to 6 hydroxy groups, b) boric acid or a boron equivalent to boric acid, which can react with the polyhydroxy compound, the weight ratio a: b being less than 1 and the composition having a pH value of 7.5 - 11.0. 2. A composition according to claim 1, characterized in that the weight ratio a: b varies from 0.5 to immediately below 1. 3. A composition according to claim 1 or 2, characterized in that the polyhydroxy compound is 1,2-propanediol, ethylene glycol, erythritan, glycerol, sorbitol or mannitol or a mixture of these substances. 4. A composition according to claim 1 or 2, characterized in that the boron equivalent of the boric acid consists of boron oxide, borax or alkali metal ortho, meta or pyroborate. 5. A composition according to any one of claims 1 to 4, characterized in that the polyhydroxy compound is present in an amount of 5 to 15% by weight in the finished composition. Composition according to any one of claims 1 to 5, characterized in that the composition has a pH value of 8.5 - 11.0. ' Composition according to any one of Claims 1 to 6, characterized in that the composition contains from 0.001 to 10% by weight of the weight of the finished composition of proteolytic, amylolytic or cellulolytic enzymes or mixtures thereof, from 10 to 60% by weight of active detergent material. and from 5 to 70% by weight of water. \ 1 <1 ._ \ m m oo 'i -ß- 10 Composition according to any one of claims 1 to 7, characterized in that the composition contains a bacterial proteolytic enzyme with a pH optimum of between 8 and 12.