FI61716B - ENZYMER INNEHAOLLANDE VATTENHALTIG FLYTANDE DETERGENTKOMPOSITION SOM UPPVISAR AENNU BAETTRE LAGERHAOLLBARHET - Google Patents

Description

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English-England (GB) 453 ^ 5/76 (71) Unilever NV, Burgemeester s'Jacobplein 1, Rotterdam, Dutch-Dutch (NL) (72) Jiri Hora, Vierpolders, Gerardus Adrianus Antonius Kivits, Helle-voetsluis, Dutch Holland (NL) (7 * 0 Leitzinger Oy (5 * 0 Aqueous liquid detergent composition containing enzymes with better shelf life - Enzymer innehällande vat-tenhaltig flytande detergentkomposition, som uppvisar ännu bättre lagerhällbarhet

The present invention relates to a liquid detergent composition containing enzymes with improved storage stability.

Liquid detergent compositions are well known in the art, and following the renewed interest in the addition of enzymes to detergent compositions, many proposals have been made in the art for enzyme-containing liquid detergent compositions.

Despite these proposals, liquid detergent compositions containing such enzymes have not entered the market to a significant extent, mainly due to the severe instability problems that occur when adding enzymes to liquid detergent compositions. This problem is recognized in the art and it has been suggested, for example, that the instability of enzymes in liquid detergent compositions be reduced by the addition of stabilization systems to such compositions. For example, it has been suggested that polyols such as glycerol, sorbitol be used? in addition, Ca salts, alkoxy alcohols, di-alkyl glycol ethers and mixtures of polyhydric alcohols with multifunctional aliphatic amines. However, these systems 2,61716 are primarily intended for liquid mixtures containing enzymes having a pH from relatively acidic to slightly alkaline.

It has now been found that the storage stability of aqueous liquid mixtures containing enzymes can be significantly improved by also adding an effective amount of a stabilization system containing a) 2-25% by weight of the final mixture of a multi-functional amino compound having at least one amino group and at least two hydroxyl groups; b) 0.25 to 15% by weight of the final mixture of boric acid, boron trioxide, borax or sodium ortho-, meta- or pyro-borate capable of reacting with a multifunctional amino compound.

The multifunctional amino compounds of the invention are aliphatic organic compounds containing at least one amine moiety and at least two hydroxyl groups. It should be noted that the term "multifunctional amino compounds" does not include quaternary ammonium compounds.

Typical examples of the multifunctional amino compounds according to the invention are polyalkanolamines, such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, and also tris (hydroxymethyl) aminomethane.

The multifunctional amino compound is usually used in an amount of 2 to 25, preferably 4 to 15% by weight of the mixture. Triethanolamine is a recommended multifunctional amino compound in protease-containing fluids.

The boron compound is generally used in an amount of 0.25 to 15, preferably 0.5 to 10% by weight of the mixture, the boron equivalent being calculated as boric acid. The amount is preferably such that the weight ratio of the multifunctional amino compound to the boron compound (based on boric acid) ranges from 10: 1 to 1: 2, most preferably from 7: 1 to 2: 1.

A stabilization system containing a multifunctional amino acid and boric acid or its boron equivalent can be added to the liquid enzyme system either by adding the ingredients as such to the liquid or by adding a separately prepared stabilization system, e.g. Mixtures of various multifunctional amino compounds can also be used, as can mixtures of a multifunctional amino compound with a polyhydroxy compound which does not contain an amino group, for example erythritan. It has further been found that by adding sucrose up to 10% by weight, the storage stability is further improved.

The enzymes to be added may be proteolytic, amylolytic and cellulolytic enzymes as well as mixtures thereof. They can be of any origin, for example from plants, animals, bacteria, fungi and yeasts. However, their choice depends on many factors, such as the optimum pH activity and / or stability, heat resistance, the effect of active detergents on stability, builders, etc. Bacterial or fungal enzymes such as bacterial amylases and proteases, and fungal cellulases are preferred in this regard. The present invention is particularly useful for enzyme-containing liquid detergents having a pH above 7.5, especially those containing bacterial proteases having a pH optimum between 8.5 and 10.5, but it will be appreciated that the composition of the invention may be advantageously used also enzymes with a somewhat lower or higher pH optimum.

Suitable examples of such proteases are subtilisins obtained from certain strains of B. subtilis and B. licheniformis. Examples are the commercially available subtilisins Maxatase ® (ex Gist-Brocades N.V., Delft, The Netherlands) and Alcalase ® (ex Novo Industri A / S, Copenhagen, Denmark).

As mentioned above, the present invention is particularly useful for liquid detergents containing enzymes which contain enzymes having an optimum pH activity and / stability above 8.5. Such enzymes are also commonly referred to as high-alkaline enzymes.

ι · i · 4 6171 6

Particularly suitable is a protease developed by Novo Industri A / S and sold under the registered name Esperase, which is obtained from a Bacillus strain and has a maximum activity in the entire pH range of 8-12. The preparation of this enzyme and analogous enzymes is described in Novo's English Patent 1,243,784.

Time allylamylases and cellulases can also be used, for example δC-amylases obtained from a particular strain of B licheniformis bacteria and described in more detail in English Patent 1,296,839 (Novo).

The amount of enzymes in the liquid / mixture may range from 0.001 to 10% by weight, and most preferably from 0.01 to 5% by weight. This amount naturally depends to a large extent on the activity of the enzyme used.

When the liquid compositions according to the invention are detergent compositions, these liquid detergent compositions also contain, as an essential ingredient, an active detergent which may be an anionic, nonionic, cationic, zwitterionic or amphoteric detergent.

Examples of anionic synthetic detergents are salts of the following groups (including sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts): C 8 -C 20 alkylbenzenesulfonates, C 8 -C 22 primary or secondary alcohols -C olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of a pyrolysis product of alkaline earth metal citrates, for example, as disclosed in British Patent 1,082,179, C8-C22 alkyl Oyl sulphate; other examples are given in "Surface Active Agents and Detergents" by Schwartz, Perry, and Berch (Vol. I and II).

Examples of nonionic synthetic detergents are the coding products of ethylene oxide, propylene oxide and / or butylene oxide with C8-C4 alkyl phenols, C8-C18 primary F1 secondary aliphatic alcohols, C8-C18 fatty acid amides; other 6171 6 5 examples of nonionic compounds are tertiary amine oxides having one C8-C18 g2 alkyl chain.

The above reference contains further examples of nonionic compounds.

The average molar amount of ethylene oxide and / or propylene dioxide in the above-mentioned nonionic compounds ranges from 1 to 30; mixtures of various nonionic compounds can also be used, including mixtures of nonionic compounds with a low and high degree of alkoxylation.

Examples of cationic detergents are quaternary ammonium compounds, such as alkyldimethylammonium halides, but such cationic compounds are less preferred in detergent compositions containing enzymes.

Examples of amphipheroic or zwitterionic detergents are N-alkylamino acids, sulfobetanins, fatty acid condensation products with orotinic hydrolysates, but due to their relatively high cost, they are usually used in combination with an anionic or nonionic detergent. Mixtures of different types of active detergents may also be used, with mixtures of anionic and nonionic active detergent being preferred. Soaps of C8 "C22 fatty acids, as well as polymerized fatty acids (as sodium, potassium and substituted ammonium salts such as triethanolamine salts) can also be used and can have a beneficial effect on the foaming properties of the finished mixture.

The amount of active detergent varies between 10 and 60%; for example, when mixtures of anionic and nonionic compounds are used, the mutual weight ratio ranges from 1: 1 to 1:10. When soap is also present, it is present in an amount of 1 to 40% by weight.

Although liquids may contain up to 40% of a suitable builder such as sodium potassium and ammonium or substituted ammonium pyro- and tripolyphosphates, nitrilotriacetate, ether polycarboxylate, citrate, carbonate, orthophosphate, polyelectrolytes / polyelectrolytes such as polyvinyl ether. , the present invention is particularly useful in liquid detergents which do not contain bulking agents.

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The amount of water in the compositions of the present invention ranges from 5 to 70% by weight.

The liquid detergent compositions according to the invention may also contain new conventional substances, for example dirt suspending agents, hydrotropes, corrosion inhibitors, dyes, perfumes, silicates, optical brighteners, anti-foaming agents, anti-foaming agents, anti-foaming agents, anti-foaming agents emollients, oxygen-releasing bleaches such as sodium perborate-Ha or percarbonate with or without bleach precursors, buffers or the like.

The pH of the finished mixture is preferably between 7.5 and 11.0, and is adjusted, if necessary, to a value in the range by adding a suitable acidic or alkaline substance.

The invention is further illustrated by the following examples. The percentages of the examples are by weight. The growth factor for the half-life of the enzyme was determined as follows:

The growth coefficient of the enzyme half-life was determined as follows: (without stabilization system) t (stabilization system F - - = ^ included) _ t k. (Stabilization system included). .... .... ..

1 1 t / 0 (without stabilom system) t ^ 2 = time when the enzymatic activity y is half of the initial enzymatic activity.

Example I

The experiments were performed with a subtiliser-type bacterial protease, Alcalase ® ex Novo (activity 10.6 Au / g), in the following aqueous system containing: M 1 · i

'' I

61 71 6 7 0.2 M pentasodium tripolyphosphate 0.12 M dimethylglycine 1.7 g Alcalase (S 'The pH of this system was 10.0 and the temperature was 57 ° C. The rate of decrease in enzyme activity in this system was measured with and without a stabilization system and The following results were obtained: No. Additive (% by weight) Ft value 1 6% tris (hydroxymethyl) aminomethane + 6.2% borax 7.5 2 6% tris (hydroxymethyl) aminomethane + 9 .4% borax 13.7 3 10% tris (hydroxymethyl) aminomethane + 15.7% borax 23.5 4 5% tris (hydroxymethyl) aminomethane + 5% erythritanes 12.4% borax 18.6 5 10% triisopropanolamine + 8.4% borax 12.7 6 triethanolamine orthoborate (prepared from 10% triethanolamine and 12.8% borax) 5.2 7 6% diethanolamine + 5.4% borax 2.5

Example II

As in Example I, experiments were performed using a bacterial protease, Esperase® (activity 41.5 KNPU / g), in the same system but at 60 ° C.

A control mixture containing only 8.8% borax gave an F 1 value of 0.7; when triethanolamine 2.5, 7.5 or 12.5% alone was used, F 1 values of 1.0, 1.1 and 1.0 were obtained.

The following results were obtained with the systems according to the invention: 10% triethanolamine orthoborate 4.3 11 8% triethanolamine orthoborate 3.0 12 6% triethanolamine orthoborate 2.1 13 4% triethanolamine orthoborate 2.0 14 2% triethanolamine orthoborate 1.6 15 8% triethanolamine + 5.6% boron 2.6 16 8% triethanolamine + 6.8% borax 3.4 17 8% triethanolamine + 8.6% borax 3.4 18 8% triethanolamine + 10.2% borax 3.2 19 6% diethanolamine + 5.4% borax 3.2 20 8% tris (hydroxymethyl) aminomethane + 7.7% borax 1.7

Example III

The experiments were performed in the same manner as in Example I using 6 bacterial amylase (Thermamyl® ex Novo) in an aqueous system containing: 0.12 M pentasodium tripolyphosphate 0.1 M glycine 0.5 g Thermamyl (activity 450 KNU / g).

The pH was 9.95 and the temperature was 49.3 ° C. The following results were obtained: No Additive (% by weight) Ftracvc 21 2% tris (hydroxymethylamino) methane + 3.15% borax 1.4 22 6% tris (hydroxymethylamino) methane + 9.45% borax 2.4 23 10% tris (hydroxymethylamino) methane + 15.75% borax 4.6 24 6.28% triethanolamine orthborate 1.4 9 61716

Example IV

The following aqueous liquid detergent compositions containing enzymes were prepared by adding 0.5% enzyme slurry (Maxatase v 500,000, subtilisin-type bacterial protease ex Gist-Brocades, Delf, The Netherlands with an activity of 500,000 Delfi units / g) to the formulations tested in the table and assayed for storage. ° C.

No. A_B_C__D_ weight percent straight-chain C.g-Cia a * "alcohol, condensate 18 mol.

With ethylene oxide 21 21 21 21 straight chain C.-Cl 2. alcohol, condensed with 8 moles of ethylene oxide 777 7 sodium xylene sulphonate 3. 3 3 3 dimerized oleic acid 6.5 6.5 6.5 6.5 triethanolamine 10 10 10 10 lauryl alcohol, condensed with 2 moles of ethylene oxide 7 7 7 7 diethylene glycol monoethyl ether 10 10 10 10 water 30.5 25.5 20.5 15.5 stabilization system, containing boric acid and triethanolamine in a weight ratio of 2: 3, prepared separately 5 10 15 20 pH 9 9 9 9

The half-life of the enzymatic activity after 6 weeks of the week was obtained: consumed, after

The enzymatic residual activity after 11 weeks of storage was: 32% 35% 60% 70% 10 61 71 6

Example V

Example IV was repeated, but 0.5% of the bacterial protease Esperase® ex Novo (activity 9 KNPU) was used instead of Alcalase. Liquids with a pH of 9.0 gave the following results: After 9 weeks of storage, the residual proteolytic activity of products A-D was still well above 50% of the initial activity. These residual activities were 60%, 60% and 85%, respectively.

Example VI

Example V was repeated but the storage experiment was now performed at 50 ° C. Products A, B, and C reached half-lives of enzyme activity after 3 1/2, 4, and 10 weeks of storage, respectively. The residual enzyme activity of the product D was 88% after 7 weeks.

Example VII

Aqueous systems containing Sperase® (20,000 G.U./ml) were stored at 37 ° C. The half-life was determined in days using the systems below with their additives. The results are shown in the table.

pH1 Half-life in days_ + 24.8 g / l boric acid 10.5 6 + 24.8 g / l boric acid + 10% sucrose 10.5 8 + 24.8 g / l boric acid + 5% triethanolamine 10.5 9 10% sucrose + 5% triethanolamine 10.2 6 24.8 g / l boric acid + 5% triethanolamine + 10% sucrose 10.5 20 pH adjusted with NaOH

Claims (7)

An aqueous liquid detergent composition containing enzymes with improved storage stability, characterized in that the composition comprises a stabilization system comprising a) 2-25% by weight of the final mixture of a multifunctional amino compound having at least one amino group and at least two hydroxyl groups b) 0, 25 to 15% by weight of the final mixture of boric acid, boron trioxide, borax or sodium ortho-, meta- or pyroborate capable of reacting with a multifunctional amino compound. Mixture according to Claim 1, characterized in that it contains 4 to 15% by weight of component a) and 0.5 to 10% by weight of component b). Mixture according to Claim 1, characterized in that the multifunctional amino compound is a polyalkanolamine. Mixture according to Claim 3, characterized in that the polyalkanolamine is diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine or tris (hydroxymethyl) aminomethane. Mixture according to Claim 1, characterized in that it additionally contains up to 10% of sucrose. Mixture according to Claim 1, characterized in that it contains 0.001 to 10% by weight of proteases, amylases or cellulases, 10 to 60% by weight of active detergent and 5 to 70% by weight of water. Mixture according to Claim 6, characterized in that it has a pH of 8.5 to 10.5.