DE2060485A1 - Liquid biological dishwashing detergent - Google Patents

Description

DlPL-PHYS. M. BECKER

PATENT ADVOCATE! N

7 STUTTGART-S

PFAFFENWEG 53 - TEL. 600300

A 1672

Kronwitter ft Co "

CH-6300 Zug Landhausweg 9

Organic liquid dishwashing detergent

The invention relates to liquid biological detergents, cleaning agents and dishwashing detergents,

In recent years, enzymes have been increasingly used in powder detergents and cleaning agents together with surfactants. Nan knows that enzymes can be kept for a long time without any noticeable loss of activity when dry and stored appropriately. More highly purified enzymes are

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more stable than raw or less well purified enzymatic substances. In dry detergents (powders or granules) are Enzymes are stable for at least 12 months when stored and packaged appropriately and when nonionic and / or cationic detergents are used.

It was previously not possible to make enzymes stable in aqueous solutions because they are inactivated within a few hours as a result of autolysis. Especially liquid detergent preparations but are well suited for washing textiles and washing dishes. Liquid detergents and dishwashing detergents (cleaning and rinsing detergents) are also preferred because they are in caking less in a damp environment and are often easier to handle and dose for cleaning or rinsing.

It is known that anion-active detergent substances are incompatible with enzymes and the reaction of the enzyme with the Substrate (e.g. laundry soiling, starch deposits on glass, etc.) by blocking the enzyme-active groups. The anionics, which act as an artificial inhibitor, occupy it the active groups of the enzyme molecule · The degree of folding of the polypeptide chains is reduced; this allows the active groups of the Enzyme surfaces do not become effective. The high capacity of the enzymes characteristic of the enzymatic effectiveness occurs only after the ionogenic or homeopolar linkage of these groups with the high molecular weight protein content Appearance,

So it can be explained that amylolytic and / or tryptic enzymes in aqueous solutions, especially in the presence of

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anion-active, concentrated surfactants or mixtures of anionic and non-anionic surface-active substances, e.g. in liquid detergents or liquid dishwashing detergents, become unstable within a few hours not possible to use liquid enzymatic detergent preparations with sufficient washing and cleaning power.

The invention is based on the object of liquid enzymatic To create detergents and detergents which have an excellent washing and rinsing effect and which last for a long enough time stay stable"

In the case of a liquid detergent, cleaning and dishwashing agent, this object is achieved in that the enzymes are clearly water-soluble. Tests have shown that such enzymes produced using a special process are capable of removing the hash or cleaning material and the substrates Contains protein, fat, starch or the like, easy to clean "Especially in dishwashers, it is very important that starch deposits are completely removed from the dishes in the final washing process, as they accumulate later." Especially when using pure, clearly water-soluble amylases Starch residues completely removed «The amylases are ^J ~ - dissolved beforehand in aqua distillata and added to the rinse aid«

For washing purposes and for a dishwashing detergent for manual purposes the use of trypsin and / or chymotrypsin produced from the pancreas has proven to be particularly advantageous In fact, additives have a skin-caring effect because they

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break down protein such as calluses, skin scraps, etc., so that the skin is smooth and soft after washing or rinsing. The pores of the skin are opened, which results in better blood flow to the skin. Bacterial proteinases, on the other hand, are for Such manual dishwashing detergents are unsuitable because experience shows that they also contain natural protein, i.e. the substance is also living Cells, attack.

For the purpose of stabilization, the addition of α-amino carboxylic acids is particularly suitable, and the liquid cleaning agent can be kept stable for at least 12 months without a drop in activity even in the presence of anionic substances. Suitable additives are, for example! Alanine, cystine, leucine, Glycocolla, serine and valine or a mixture of glycocolla and glutamine in a ratio of 1: 1 or also glutathione or insulin, Even in the presence of the well-known "enzyme poisons" such as Dodecylbenzenesulfonate and fatty alcohol or fatty alcohol sulfates retain their enzymatic activity.

Glutathione can also be used in place of the ° C-aminocarboxylic acids mentioned (Tripeptide) can be used alone «It occurs as a coenzyme in individual enzyme reactions, whereby the sulfhydryl group can be reversibly oxidized and reduced. Because of these properties, the tripeptide acts as a biological redox system.

For a perfect effect it is necessary that only the purest, clearly water-soluble inhibitor-free enzymes, that is, free of low molecular weight accompanying proteins are used. at The use of crude or poorly purified enzymes would, as tests have shown, reduce the protective effect within a short time

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of the oC-aminocarboxylic acids and thereby the activity of the The enzymes used are reduced «Insoluble enzymes are not suitable because they are active in the presence of detergents Substances lose their activity and also cause a very slimy sediment when used in liquid cleaning agents, which is particularly noticeable in bacterial proteinases «

An essential part of the invention is to be clearly water-soluble To keep enzymes stable in more or less concentrated surfactant liquids «

Amylases are suitable as clear water-soluble enzymes, the one Have activity of about 1,000 to 10,000 Willstatter units, or trypsin and / or chymotrypsin with an activity of approx "44 to 450 Willstätter units"

If used for technical purposes, GIykokoll will be used alone or a mixture of glycocolla + oC-aminoglutaric acid in the ratio 2il suggested, since these preparations are cheap in large quantities can be produced synthetically «

In the manufacture of the detergent, cleaning agent or dishwashing agent it must be ensured that when using glycocolla or the above-mentioned amino acids as protective colloid for the water-soluble enzyme, the hydrophilic groups of the washing-active substances used absorb the added deionized water should have before glycocolland the water-soluble enzyme are added «If this sequence were changed, the protective colloid effect would not be fully achieved because in the beginning

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Intermediate rapid decay in the presence of detergents Substances takes place «

The enzymes used in the present invention are obtained from animal organs, namely the pancreas of pigs or cattle, won.

In the following, the invention is to be explained by means of examples, the quantitative data, soft n not being stated otherwise, relates to weight

example 1

The following mixture has been found for a biological rinse aid (rinse aid) for dishwashers proven to be suitable:

20 - 35 kg surfactants, e.g. alkylphenol poly-

glycol ether or fatty alcohol polyglycol ether or a mixture of these two in a ratio of 1: 1,

70 1 distilled water, 0.5 - 1 kg glycol,

0.02 - 0.03 kg OC-Amylase, pure, clear water-soluble,

20 ml fragrance,

Proportion of citric acid, so that the pH is 6.5 to 6.8.

The quantitative use of surfactants is based on 100% detergent substance. The pH of a one percent Solution of the concentrate should be in the range of 6.5 - 6.8, the addition of citric acid depends

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on the pH value of the washing-active substances «The washing-active Substances for a rinse aid are basically non-ionic, so the addition of glycocolla can be relative are kept low «The amount of enzymes added depends on the level of activity required.

Example 2

Liquid dishwashing detergent for manual use

15-20% dodecylbenzenesulfonate,

5% fatty alcohol sulfate,

1.5 - 2% glycocolla,

0.01% trypsin / chymotrypsin, clear water-soluble,

5% sodium hexametaphosphate,

50 g fragrance,

! test water (tap water)

The pH value of a one percent solution should not exceed or fall below 7.5 (for a temperature of 40 C) «

As explained above, this hand washing-up liquid also has a skin-caring effect due to the addition of trypsins Effect"

It has been shown that stains containing protein on textiles and / or dishes as well as residues of proteins, Fats and the like, completely with the means described to be removed «

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As stated above, the clearly water-soluble enzymes described are preferably from animal pancreas, in particular - because of the greater yield - obtained from pig pancreas. As a result of the self-digestion of these organs it is It is important that the pancreas is removed immediately after slaughtering the animal and frozen at temperatures of around -15 C to -30 C. “Then the pancreas is crushed in the frozen state and treated with high-proof, approx. 95% alcohol by volume poured over and stirred slowly while avoiding an emulsion formation. After stopping this approach for about The preparation is placed on a suction filter for 24 hours and a precipitate consists of pancreatic fiber material, obtained, which supplies trypsins, chymotrypsins and lipase, while pure oC-amylase with an activity of approx. 10,000 Willstätter units are won.

The extract is diluted with tap water, stirred and then left to stand at approx. 5 C for several hours. The clear liquid is then decanted off, A light brown powder remains as a residue, which can be air-dried directly and consists of highly active OC amylase. Preferably the residue is taken up before drying

Cooled 0 ° C, with a mixture of ethanol and acetone im

Ratio 1 * 1 mixed and at a temperature of 0 C washed, then filtered again and, after removing the solvent, the residue is air-dried.

The precipitate consisting of pancreatic fiber material is preferred washed with acetone and dried! It produces active pancreatin, which consists of lipase, trypsin and chymotrlpsin.

209814Π% 82

The method is explained in more detail below using an exemplary embodiment:

Example 3

60 kg of pig pancreas is obtained immediately after slaughter Frozen at temperatures of approx. -15 to -30 ° C and in the frozen state through a meat grinder with 3 - 5 mm Rotated perforated disc

The crazy amount of pancreas is in the plastic drum given and doused with 133 1 95% ethyl alcohol and stirred slowly. 75 liters of tap water are then added so that the ethyl alcohol is diluted to 50% by volume will. The batch remains covered for about 24 hours at room temperature.

After this time has elapsed, the mixture is stirred again and the entire batch is placed on a suction filter. Here is won:

a) an extract,

b) a precipitate consisting of pancreatic fiber material,

The extract is mixed with tap water to a total of 200 1 diluted, stirred for 10 minutes and then left to stand for approx. 3 hours at + 5 ° C. After that, the liquid becomes clear decanted off and poured the mass onto a suction filter. The filter residue consists of light brown

209 * 4 ¥ / f38l - ίο - ·

- OK -

Powder that is air dried on filter paper. He exists the end

900 g of highly active oC amylase with one activity of approx. 10,000 Willstätter units per g / substance,

The precipitate, consisting of pancreatic fiber material, becomes Doused with acetone and dried. Approx. 700 g are obtained active pancreatin that

20 units of lipase,

40 units of trypsin,

60 units of chymotrypsin

per g / substance contains «

Before the enzyme enters the liquid washing, cleaning or cleaning agent Dishwashing detergent is added, it is dissolved in distilled water, with 25 mg being dissolved in 10 ml. It shows no opalescence,

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Claims (1)

Claims 1, Liquid biological detergents, cleaning agents and dishwashing detergents, which contain surfactants and haters, characterized that they contain clearly water-soluble enzymes « 2 «Liquid biological detergents, cleaning and dishwashing agent according to claim 1, characterized in that the enzyme is Amyläse and preferably an activity of ca, 250 to 10,000 Will- M Stätter units having" 3 «Liquid biological detergents, cleaning agents and dishwashing detergents according to claim 1, characterized in that the enzyme is a proteolytic enzyme such as trypsin and / or chymotrypsin and preferably has an activity of approx. 40 to 450 Willstätter units " 4 «Liquid biological detergents, cleaning agents and dishwashing detergents according to one of the preceding claims, characterized by the addition of OC-aminocarboxylic acid as a stabilizer « 5 «Liquid biological detergents, cleaning agents and dishwashing detergents according to claim 1, 2 or 3, characterized by the addition of alain, cystine, leucine, glycocolla, serine, valine or insulin « 6 «Liquid biological detergents, cleaning agents and dishwashing detergents according to claim 1, 2 or 3, characterized by the addition of glycocolla and glutamine in a ratio of approx. ItI. - 12 2098U / 1382 7, liquid biological washing, cleaning and dishwashing detergents according to claim 1, 2, 3 or 4, characterized by the addition of glutathione (tripeptide) ₍ 8, Liquid biological detergents, cleaning agents and dishwashing detergents according to claim 1, 2 or 3, characterized by the addition of glycocoll alone or glycocoll + OC-aminoglutaric acid im Ratio 2: 1, 9, Liquid biological detergents, cleaning agents and dishwashing detergents according to one of the preceding claims, characterized in that they have a pH value of 6-8, 10, Process for the production of clear water-soluble enzymes for Use in liquid washing, cleaning and dishwashing detergents according to claim 1, characterized in that one Immediately after slaughtering the animal, keep the animal pancreas at a temperature of approx. -15 C for at least 24 hours Cools down to -30 C, crushed in the frozen state, then mixed with about 95% alcohol by volume, avoiding the formation of an emulsion, then with tap water to an alcohol concentration of about 50% by volume and the mixture is left to stand at room temperature for at least 24 hours, after which time the pancreatin precipitate consisting of pancreatic fiber material is separated and dried and from the extract freed from the pancreatin leather lump after dilution and Mixing with tap water and leaving to stand at approx. 5 ° C, a residue consisting of α-amylase is isolated. - 13 2098U / 138? 11, the method according to claim 10, characterized in that one the frozen pancreas mixed with 95 vol% igera ethyl alcohol after the chopping » 12 «The method according to claim 10, characterized in that one the precipitate of od-amylase isolated from the extract after cooling to 0 ° C with a mixture of ethanol and acetone in the ratio 1x1, filtered off and then dries 13 «Method according to claim 12, characterized in that 25 mg of the residue consisting of oC amylase in 10 ml aqua destillata are dissolved, 14 «Method according to claim 10, characterized in that the precipitate is dried with acetone. 2098U / 1382 -