FI61715C - ENZYMER INNEHAOLLANDE STABILIZERAD FLYTANDE DETERGENTKOMPOSITION - Google Patents

Description

R3F «] [B] (11) NOTICE OF ADVERTISEMENT '- A lJ' 'UTLACGNINOSSKRIFT 6 I / 15 C Patent oy'inetty 10 09 1982' 'Patent meddelat (5η Kv.ik? /Int.ci.3 c 11 D 7 / 42 FINLAND — FINLAND W PtttnttlhakeiiMi · - Ptt «nUn * 6knlng 773177 (22) Hakamiiptlvl - AmMcnlngidag 25.10.77 * * (23) Alkuptlvi— Glklgh« t * dtg 25.10.77 (41) Tullut JulkiMka! - Bllvlt 02mlt! _.,. (44) NlhtivIkilpMon] · kuL | ullutiiun pvm.— οί ac fto

Patent- och ragistarstyralaan 'Amoku utlagd och «i.skrwt * n pubiicurad ^' '' (32) (33) (31) ttuolkwit —B« gtrd priorltut 01.11.76

England-England (GB) 1 + 5344/7 fa (71) Unilever N.V., Burgemeester s 1 Jacobplein 1, Rotterdam, Holland-Holland (NL) (72) Jiri Hora, Vierpolders, Gerardus Adrianus Antonius Kivits,

Hellevoetsluis, Holland-Holland (NL) (7l +) Leitzinger Oy (54) Stabilized liquid detergent composition containing enzymes - Enzymer innehällande stabiliserad ilytande detergentkompositiön

The present invention relates to an aqueous liquid detergent composition containing enzymes with improved storage stability, comprising a stabilization system comprising a) 4-25% by weight of the final mixture of one or more polyhydroxy compounds having only C, H and O atoms, and having 2 to 6 hydroxy groups; and b) boric acid, boron oxide, borax or alkali metal ortho, meta or pyroborate,

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 proposed, for example, that the instability of enzymes in liquid detergent compositions be reduced by adding stabilization systems to such compositions.

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For example, in Japanese Patent Application 47/35, 192 ((Chem.

Abstr. Butter. 78/1973) ref. 70214g) it is known that granular, stabilized enzyme selectors, including liquid detergent compositions containing enzymes, are prepared by adding a combination of polyalcohols and borax. According to the description of said Japanese patent application, at least 5% by weight of the final mixture, preferably 10 to 30% by weight, is used, these olole alcohols, exemplified by sorghol and glycerol. Borax is used in at least 20%, preferably 50-100% by weight of polyalcohol. The mixture should thus have a weight ratio of polyalcohol to borax equal to or greater than 1.

In addition, the pH of the mixtures according to this previous proposal is between 3.9 and 7.4, which was demonstrated experimentally by repeating Example 1.

It has now been found that the storage stability of the above-mentioned liquid detergent compositions containing enzymes having a pH of more than 7.5, preferably between 8.5 and 11.0 (at 25 ° C), can be significantly improved by the weight ratio of the invention so that the weight ratio a : b, where b) is calculated as borax, is less than 1 and the pH of the mixture is 7.5 to 11.0. Compared to the combinations of the above-mentioned Japanese patent application, the enzyme stabilizing effect of the systems of the present invention is significantly better.

Polyhydroxy compounds suitable for use in the present invention contain only C, H and O atoms. They do not contain other (functional) substituent atoms, such as N-, S- and the like. 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 well suited for use in the present invention include diols such as 1,2-propanediol, ethylene glycol, erythritane, polyols such as glycerol, sorbitol and mannitol.

The polyhydroxy compound is usually present in an amount of at least 4% by weight of the final mixture, up to 21% by weight.

The amount is preferably between 5-15% by weight of the final mixture.

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Boric acid or a boron equivalent thereof such as boron trioxide, borax or other alkali metal borates capable of reacting with a polyhydroxy compound such as sodium, ortho, meta- and pyroborates is used in an amount such that the weight ratio of polyhydroxy compound to boron is less than that of boron. This means that the boron compound is used in more than 100% of the amount of the polyhydroxy compound. The amount generally ranges from> 100 to 200% by weight and most preferably> 100 to 160% by weight of the polyhydroxy compound.

The weight ratio of polyhydroxy compound to boric acid or its equivalent is less than 1, generally between 0.5 and slightly less than 1.

Liquid mixtures containing enzymes to which the stabilizing systems of the invention are added may be aqueous liquid systems, for example simple solutions, but are most preferably aqueous liquid detergent mixtures containing as essential ingredients enzymes, active detergents and water. The pH is above 7.5, preferably between 8.5 and 11.0, or the pH has been adjusted as such by any suitable means.

The enzymes to be added may be proteolytic, amylolytic or cellulolytic enzymes as well as mixtures thereof. They can be of any origin, for example from plants, animals, bacteria, fungi and yeast. However, their choice depends on many factors, including the optimum pH activity and / or stability, heat resistance, the effect of active detergents on stability, builders, etc. Bacterial and fungal enzymes are preferred in this regard, such as bacterial amylases and proteases and fungal cellulases. . The present invention is particularly useful for enzyme-containing liquid detergents containing bacterial proteases having a pH optimum between 8.0 and 11.0, but it will be appreciated that enzymes having a somewhat lower pH optimum may also be advantageously used in the compositions of the invention. or higher.

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

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As mentioned above, the present invention is particularly useful for enzyme-containing gaseous detergents containing enzymes having an optimum pH activity and / or stability above 8.0. Such enzymes are also commonly referred to as high-alkaline enzymes.

Particularly suitable is a protease developed by Novo Industri A / S and sold under the registered trade name Es p eras e OiP, 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.

Alkaliylases and cellulases can also be used, for example α-amylase obtained from a particular strain of B. licheniformis and described in more detail in British 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.

The liquid detergent compositions of the invention further contain as an essential ingredient an active detergent which may be an alkali metal or alkanolamine soap of a C1Q-C24 fatty acid, including polymerized fatty acids or an anionic, nonionic, cationic, zwitterionic or amphoteric synthetic of these.

Examples of anionic synthetic detergents are the salts of the following groups (including sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts): C9-C20 alkylbenzenesulfonates / C8 ”C22 C8-C24 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of a pyrolysis product of alkaline earth metal citrates, for example as disclosed in British Patent Publication 1,082,179, C8-C22 alkyl oxide sulfates, other examples are given in Sclvartz,

In "Surface Active Agents and Detergents" by Perry and Berch (Vol. I and II).

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Examples of non-ionic synthetic detergents are the condensation products of ethylene oxide, propylene oxide and / or butylene oxide with C8-C8 alkyl phenols, C0-8 8 primary or secondary aliphatic alcohols, C8-C8 g fatty acids! di en with; other examples of nonionic compounds are tertiary amine oxides having one C 1 -C 6 alkyl chain and two C 1-6 alkyl chains. The above reference contains further examples of nonionic compounds.

The average molar amount of ethylene oxide and / or propylene oxide 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 amphoteric or zwitterionic detergents are N-alkylamino acids, sulfobetanins, fatty acid condensation products with protein 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 (as sodium, potassium and substituted ammonium salts such as triethanolamine salts) of ciq C24 fatty acids, as well as polymerized fatty acids, may also be used, preferably in combination with an anionic and / or nonionic synthetic detergent. They 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-6 61715 and tripolyphosphates, nitrilotriacetate, ether polycarboxylate, citrate, carbonate, orthophosphate ethylene ethylene / polyelectrolytes such as polyelectrolytes, ., the present invention is particularly useful in liquid detergents which do not contain bulking agents.

The amount of water in the detergent compositions according to the invention varies between 5 and 70% by weight.

The conventional detergent compositions of the invention may also contain other conventional agents, 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 substances, oxygen-releasing bleaches such as sodium perborate or percarbonate with or without bleach precursors, buffers and the like.

The pH of the finished mixture is higher than 7.5 and should preferably be between 8.5 and 11.0 and, if necessary, buffered to a range of values by the addition of a suitable buffering system (e.g. with dimethylglycine).

The invention is illustrated by examples. The percentages of the examples are by weight. The increase in the half-life of the enzyme was determined in the examples as follows: A sample was continuously removed from the test solution, which was continuously diluted (1: 200) and whose enzymatic activity was determined continuously (casein was used as a substrate for proteolytic activity). The logarithm of the residual activity was shifted against time and the first-order rate constant K i was calculated. >,

The growth factor Ft of the enzyme half-life is determined as follows: 1 * 61715 K * (without stabilization system) t _ (stabilization system = = ___ mttkäna) _ K. (stabilization system included) χ v / 2 d ^ -man stabilization system) ty / 2 = time at which the enzymatic activity y is half of the initial enzymatic activity.

Example I

In this example, aqueous systems containing

O

bacterial protease, Alcalase ex Novo. The aqueous systems contained per liter: 0.2 moles of pentasodium tripolyphosphate 0.12 moles of dimethylglycine 1.7 g of Alcalase® (activity 10.6 AU / g).

The pH of the solution was 10 and the temperature 57 ° C. The rate of decrease in enzyme activity was measured in this system with or without stabilization systems, as shown below, and the growth factor for the half-life of the enzyme was determined. The following results were obtained.

61715 „„ Stabilization system.: I i Quantity Ratio Ft value

N: ° ^ wt% X P

—P D B

Polyhydroxy-Borax compound (P) (B) 1 Ethylene glycol + 10 15.4 0.649 16.7 2 + 6 9.2 0.652 8.3 3 "- 10 - 1.9 4 Glycerol + 10 10.3 0.970 14 .7 5 "- 10 - 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 10 Mannitol! + 10 10.5 0.952 3.2 11 "+ 10 5.2 1.923 2.3 12" - 10 - 1.8 These results show that using the stabilization system of the invention, F 1 values increased. Experiments Nos. 8 and 11 p are not in accordance with the invention, (= ratio> 1) and show that the

By making these ratios, the F. values are significantly reduced compared to p = · ratios <1. Experiments Nos. 7 to 9 and 10 to 12 show that by reducing the B p = ratio, better F-values are obtained, contrary to previous doctrine in the art that the g-ratio must be> s 1. Using borax alone (not added no polyhydroxy compound) 2%, 4%, 8% and 9.45% gave the following Ffc values: 1.0, 1.3, 1.8 and 2.4.

Example II

The bacterial protease "Esperase" ®ex Novo (activity 41.5 KNPU / g) was used in this series of experiments. The water system was identical to Example I, but the temperature was now 60 ° C. Using 4% erythritan p and 7.4% borax (- = 0.54), a Ft ~ value of 2.5 was obtained.

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Example III

Systems containing bacterial α-amylase (Termamyl®) were tested in the same manner as in Example I. The aqueous system contained: 0.12 moles of pentasodium triplyphosphate 0.1 moles of glycine 0.5 g of Thermamyl R (activity 450 KNU / g).

The pH was 9.95 and the temperature was 59.3 ° C. Using the stabilization system,

P

containing 6% ethylene glycol + 9.2% borax (g ratio 0.65) gave a Ft ~ value of 2.2.

Example IV

Example I was repeated using a stabilization system containing 10% glycerol and various amounts of borax. The following results were obtained:

Glycerol Borax (%) P / B ratio F

a) 10% in all places 14 0.71 11.6 b) 12 0.83 12.8 c) 11 0.91 14.1 d) 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) 52 3.4 j) 2.5 4 2.3 k) 0 1.8

Claims (7)

61 71 5 10 An aqueous liquid detergent composition containing enzymes with improved shelf life, comprising a stabilizing system comprising a) 4-25% by weight of a final mixture of one or more polyhydroxy compounds having only C, H and O atoms and having: 2 to 6 hydroxy groups; and b) boric acid, boron oxide, borax or alkali metal ortho, meta or pyroborate, characterized in that the weight ratio a: b, where b) is calculated as borax, is less than 1 and the pH of the mixture is 7.5 to 11.0 . Mixture according to Claim 1, characterized in that the weight ratio a: b is between 0.5 and slightly less than 1. Mixture 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 thereof. Mixture according to Claims 1 to 3, characterized in that 5 to 15% by weight of the polyhydroxy compound is present in the final mixture. Mixture according to Claims 1 to 4, characterized in that the pH of the mixture is 8.5 to 11.0. Mixture according to Claims 1 to 5, characterized in that the mixture contains 0.001 to 10% by weight of the final mixture of proteolytic, amylolytic or cellulolytic enzymes or mixtures thereof, 10 to 60% by weight of active detergent and 5 to 70% by weight of water. Mixture according to Claims 1 to 6, characterized in that it contains a bacterial proteolytic enzyme having a pH optimum of between 8 and 12.