DE2058826A1 - Liquid stabilized enzyme preparations which can optionally be used as washing or cleaning agents - Google Patents

Description

1) Proteases and / or amylases in such amounts that the activity of the stabilized enzyme preparation is in the range from 1000 - 8OO 000, preferably from 10 000 - 800 000 PU / ml and / or TO - 10 000, preferably 200 - 10 000 SKBE / ml lies. ^:

2) 1 - 45 wt. ~ 2> at least one of the water-soluble organic compounds listed under a) to d):

a) Dihydric to hexahydric aliphatic alcohols with a maximum of 8, preferably a maximum of 6 carbon atoms per molecule and / or polyethers of these polyhydric alcohols and / or partial ethers derived from these polyhydric alcohols and containing at least one hydroxyl group in the molecule with monohydric C. u-Pilkoholent

b) Carboxylic acid or phosphoric acid alkyl containing 2-8, preferably 2-6 carbon atoms in the molecule or -hydroxyalky! amide,

209824/0843

Henkel & Cie GmbH se ». 2 to the ratentanm.idun »d 4046

c) Heterocyclic compounds which may contain hydroxyl groups and have a maximum of 8 carbon atoms

in the molecule with a hetero oxygen and / or hetero oxygen atom,

d) Dialkyl sulfoxides with 1-4 C atoms in the alkyl radicals,

3) 1 - J> 0 wt .- ^ at least one of the water-soluble organic compounds listed under e) - g):

e) aliphatic or alicyclic hydroxyalkylamines, which have a maximum of 8, preferably a maximum of 6, carbon atoms per hydrocarbon radical, as well as their

. Ether with C. u alcohols,

f) Heterocyclic compounds optionally containing hydroxyalkyl groups and having a maximum of 8 carbon atoms in the molecule with hetero oxygen and / or hetero nitrogen atom,

g) 2-8, preferably 2-6 carbon atoms in the molecule containing carboxylic acid or phosphoric acid alkyl or hydroxyalkylamides,

however, a compound of group 2 b only with a compound of groups 3 e or f or one compound of group 2 c can only be combined with a compound of groups e or g,

4) 0 - 30, preferably 1-30 wt .- ^ of a carboxylic acid ψ or hydroxycarboxylic acid with a maximum of 6 carbon atoms or

a water-soluble salt of this acid with organic or inorganic cations,

B) other common ingredients of detergents and cleaning agents and, if applicable, water,

the enzyme preparations or the detergents and cleaning agents containing them have a pH of 3-10. //i

209824/0843

Henkel & Cie GmbH s · »· 3 w Pat« in registration d 4046

The invention relates to a further embodiment of the enzyme preparations of the main patent. The liquid stabilized enzyme preparations according to the invention are characterized by that the aliphatic or alicyclic hydroxyalkylamines according to point 3 e) of the main patent in whole or in part -water-soluble, hydroxyl group-free di- or polyamines or by aliphatic or alicyclic, hydroxyalkyl groups containing di- or polyamines and / or the heterocyclic compounds optionally containing hydroxyalkyl groups at most 8 carbon atoms in the molecule with hetero oxygen and / or hetero nitrogen atom according to point 3 f) of the main patent or partially by appropriate connections with at least another basic nitrogen atom in the molecule have been replaced.

Accordingly, the compounds to be used according to the invention as stabilizer components according to point 3 e) or point 3 f) of the definition of the invention - apart from the water-soluble, hydroxyl-free di- or polyamines - can be understood as derivatives of the compound types mentioned in the main patent, which additionally contain at least one further basic nitrogen atom contain. These further basic nitrogen atoms can be of a primary, secondary or tertiary nature; they can also be present as part of a heterocyclic ring system. As with the corresponding compounds of the main patent, the alkyl, alkylene, cycloalkyl or cycloalkylene radicals present in the stabilizer components to be used according to the invention can contain up to 6 carbon atoms in an uninterrupted CC bond. A selection of useful substances according to the invention can be found in the ispielen B _e. There they are roughly arranged according to decreasing effectiveness, although certain shifts may result depending on the length of the test duration and the concentration of the individual components and the stabilizer component 2a--2d present in each case.

2098 2.4 / 0843 - 4 - &

BAD OWGtNAL

Hang! & Cie GmbH Since "4 to the patient> M £ inm" ldim _a D 4046

The following compounds have proven to be particularly effective: i-Cyclohexylamino - ^ - aminopropane, 1-aminomethyl-2-aminocyclopentane, N-methylimidazole and 2-methylimidazole. There but some of the less effective components are technically more accessible than those of higher effectiveness, In practice, especially from an economic point of view, there are some easily accessible connections with low effectiveness are of greater practical importance than more difficult to access compounds with greater Effectiveness. These compounds which are particularly important in practice include: 1,2-propylenediamine, 1-dimethylamine or 1-diethylamino-propylamine-J, bis- (3-aminopropyl) -methylamine, Diethylenetriamine, triethylenetetramine, tetraethylene pentamine, N-hydroxyethyl ethylenediamine.

In addition, the information in the main patent also applies accordingly to the additional patent., Ί / χ

209824/0843

Henkel & Cie GmbH s.it. 5 ^to Poientonm.idune d 404-6

Examples

The following examples describe compositions of some preparations according to the invention and, for comparison, also the compositions of some preparations of the composition not claimed.

To produce the enzyme concentrates described in the examples - unless expressly stated otherwise - a solid, uncut enzyme concentrate obtained in the industrial production of enzymes ("Protin A stock enzyme" from Daiwa Kasei, Japan) in an aqueous solution Dissolved buffer solution containing 11.25 g / l KHgPO ^ and 20.00 g / l Na ₂ HPO _2,. Contained 12 HpO. The amines were first mixed with enough acetic acid in the presence of a little water that the pH of this mixture was also 6.5. Both solutions, the enzyme solution and the amine solution, were then mixed with the addition of the other ingredients.

To demonstrate the stabilizing effect achieved according to the invention, comparative solutions in which at least one the stabilizing components required according to the requirements have been replaced by the same amount of aqueous buffer solution was, so that all the solutions to be compared with one another the- ■ had the same enzyme concentration and pH. The ™ The pH value was always measured on the undiluted concentrates.

To test the storage stability, about 1) 0 ml of these solutions were kept for a certain time at 37 ° C. in a closed ground glass stopper after adding 0.1 ml of toluene. The enzyme activity was then determined; the results can be seen from the tables, / ^

209824/0843

Henkel & Cie GmbH S.it. 6 mr PoMntanm.ldung Ο 4046

For the technical production of the products according to the invention it is expedient to replace the toluene with an appropriate one Amounts of known anti-scaling substances, for example by those mentioned in the main patent.

While the amines in the investigated preparations are called acetic acid If salts were present, the amine-free concentrates investigated as comparison products did not contain any acetate ions. All investigated concentrates, with or without amine, had a pH value of 6.5

w The amount missing from 100% by weight in the recipes is water.

The amines marked with (+) in the tables are particularly interesting because of their easy accessibility, i.e. themselves if they show a significantly lower stabilizing effect than other amines in the selected concentration, so they come into question for practical use, because the amount used is one with consideration of their lower price increase and so can come to better stabilizing effects., ^

20982A / 08A3

Henkel & Cie GmbH

Since 7 ^Iur patent application D 4046

Example 1

A liquid enzyme concentrate has the following composition:

2 wt .- ^ dry enzyme preparation corresponding to an activity

did of 50,000 PU / g liquid enzyme preparation 11 wt .- ^ glycerol-rf-monomethyl ether 11 wt .- ^ di- or polyamine
10 wt -.% Acetic acid
15 wt .- ^ 0.35 M aqueous phosphate buffer solution pH = 6.5

The following table contains information about the stability of this enzyme concentrate and other enzyme concentrates that are not claimed:

Diamine or polyamine caseinolytic residual activi
ity in <f> of the comparison
preparation after χ weeks
Store at 37 ° C χ = 12 weeks χ = 6 weeks 86 1 -Cyclohexylamino ^ -aminopropane 91 83 i-aminomethyl-2-aminocyclopentane 91 76 Tripropylenetetramine 88- 71 Ν, Ν-dimethylethylenediamine 83 68 Tetrapropylene pentamine 82 . 74 1,2-cyclohexanediamine 80 - 1,2-propylenediamine (+) 80 - Pentamethylenediamine 79 77 1-methylamino-3-aminopropane 76 77 Polyethylene polyamine (mol. ~ Wt. 600) 76 75 Bia ~ (3-aminopropyl) -methylamine (+) 74 70 Polyäthylonpolyamine (mol.wt. 1000) 82 64 N_4_Hydroxybutyryldiethyleritriamin 76 53 'N-IIydrOÄy- "i: hy.lrr: d-1 amine (+) 72 51 1-Oiäthylamj noprcpy lamin-3 (+) 70 52 1 , 4-Di ami nobutane 67 40 !!, N-Biis-iii-lv / di'oxyethyl) - 63 3 IU
- 8 - '- ■ hno / “.υ, n ^ Ki-atz 209824/0 843 6th

SAD ORIGtNAL

Henkel & Cie GmbH

Soil · ö * <"Pulentanmeldgng D Example 2

A liquid enzyme concentrate has the following composition:

2 wt .- ^ dry enzyme preparation corresponding to an activity of 50,000 PU / g liquid enzyme preparation 33 wt. % Glycerin- ° C-monome thy lather 11 wt. % Di- or polyamine
10 wt -.% Acetic acid
15 wt. Fo 0.33 M aqueous phosphate buffer solution pH = 6.5

The following table contains information about the stability of this enzyme concentrate and other enzyme concentrates that are not claimed:

Diamine or polyamine caseinolytic residual activi
in % of the comparison
preparation after χ weeks
Store at 37 ° C χ = 6 weeks Λ χ = 3 weeks 94 Diethylenetriamine 97 90 Triethylenetetramine 98 98 Tetraethylene pentamine 98 6th without added amine 11

20982 W0843

Henkel & Cie GmbH

to the Pulenlon m »! dung D

4046

Example 3

A liquid enzyme concentrate has the following composition

2 wt .- $ dry enzyme preparation corresponding to an activity of 50,000 PU / g liquid enzyme preparation 11 wt .- ^ glycerol-ee-monomethyl ether

5.5 wt. #. Diamine or polyamine
10% by weight acetic acid
15 wt .- # 0.35 M aqueous phosphate buffer solution pH = 6.5

The following table contains information about the stability of this Enzyme concentrates and other unclaimed enzyme concentrates:

Diamine or polyamine caselnolytic residual activi
activity in % of ■ comparison
preparation after χ weeks
Store at 37 ° C X = 12 weeks χ = s 6 weeks 41 1-Cyclohexylamino-J-aminopropane 64 40 1,2-cyclohexanediamine 59 34 1,4-diaminobutane 51 27 N, N ~ dimethyl-ethylenediamine 48 28 1-aminomethyl-2-aminocyclopentane 47 · 31 1-methylamino-3-aminopropane . 46 25th 1-dimethylamino-3-aminopropane (+) 38 19th Triethylenetetramine (+) 30th 17th Diethylenetriamine (+) 26th 19th Tetraethylene pentamine (+) 32 ⁵ A'tL without added amine 6th

- 10 -

209 824/084

Henkel & Cie GrnbH

Ropes

for patent application D

Example 4

A liquid enzyme concentrate has the following composition:

2 wt .- ^ dry enzyme preparation corresponding to an activity of 50,000 PU / g liquid enzyme preparation 11 wt .- $ glycerol-dT-monomethyl ether

5.5 and 11 wt -.% Of di- or polyamine 10 wt Jo acetic acid
15 wt -.% 0.33 M aqueous phosphate buffer solution pH = 6.5

The following table contains information about the stability of this enzyme concentrate and other enzyme concentrates that are not claimed:

Diamine or polyamine Wt -.% N-methylimidazole caseinolytic residual activi
in % of the comparison
preparation after χ weeks
Store at 37 ° C χ = 12 weeks Wt, - ^ 2-methylimidazole χ = 6 weeks 81 11 Wt .- ^. N-hydroxyethylpiperazine 88 79 11 Wt -.% Of 1- (3-aminopropyl) -
plperidin 88 75 11 Wt .- ^ 4- (3-aminopropyl) -
morpholine (+) 85 76 11 Wt .- ^ N-hydroxyethylpiperazine 83 " 63 11 Wt .- ^ 1-4-bis (2-hydroxypropy ^ -
piperazine • 78 64 11 Wt -.% N, N-bis (3-aminopropyl) -
piperazine 77 68 11 Wt .- ^ 1- (3-aminopropyl) -
piperidine 72 59 11 Wt .- ^ 2-methylimidazole 73 37 5.5 Wt .- ^ N-methylimidazole 59 36 5.5 without addition of atnin 58 32 5.5 53 6th

209824/0843

- 11 -

Claims (1)

Claims 1) proteases and / or amylases in such amounts that the Activity of the stabilized enzyme preparation in the range from 1000 to 800,000, preferably from 10,000 to 800,000 PE / ml and / or 10-10,000, preferably 200-10,000 SKBE / ml is. . 2) 1-45 weight -% of at least one of a) to d) listed water-soluble organic compounds: a) Dihydric to hexahydric aliphatic alcohols with a maximum of 8, preferably a maximum of 6 carbon atoms per molecule and / or polyether of these polyhydric alcohols and / or of these polyhydric Partial ethers derived from alcohols and containing at least one hydroxyl group in the molecule with monohydric ethers C | _2j. -Alcohols, b) containing 2-8, preferably 2-6, carbon atoms in the molecule Carboxylic acid or phosphoric acid alkyl or hydroxyalkyl amides j c) optionally, hydroxyl-containing hetero- cyclic compounds A having at most 8 carbon atoms in the molecule with Heterosauerstoff- and / or hetero nitrogen atom " d) Dialkyl sulfoxides with 1-4 C atoms in the alkyl radicals, 5) 1- ■ <· JO wt .- ^ one of the water-soluble substances listed under e) * - g) organic compounds: e) aliphatic or alicyclic hydroxyalkylamines, those per hydrocarbon radical at most 8, preferably have at most 6 carbon atoms, as well as their ethers with'C._j, alcohols, / - '., 5 - 12 -209824/0843 Henkel & Cie GmbH s »üe 1 2 to avoid potential d 4046 f) optionally containing hydroxyalkyl groups heterocyclic compounds with a maximum of 8 carbon atoms in the molecule with hetero oxygen and / or hetero nitrogen atom, g) 2-8, preferably 2-6 carbon atoms in the molecule containing carboxylic acid or phosphoric acid alkyl or hydroxyalkylamides, however, a compound of group 2 b only with a compound of groups 3 e or f or one compound of group 2 c can only be combined with a compound of groups 3 e or g, 4) 0-30, preferably 1-30% by weight of a carboxylic acid or hydroxycarboxylic acid with a maximum of 6 carbon atoms or a water-soluble salt of this acid with organic or inorganic cations, B) other common ingredients of detergents and cleaning agents and, if applicable, water, the enzyme preparations or the detergents and cleaning agents containing them have a pH of 3-10, characterized in that the aliphatic or alicyclic hydroxyalkylamines according to point 3 e) of the main patent are wholly or partially replaced by water-soluble, hydroxyl-free di- or polyamines or by aliphatic or alicyclic di- or polyamines containing hydroxyalkyl groups and / or the heterocyclic compounds optionally containing hydroxyalkyl groups with a maximum of 8 carbon atoms in the molecule with hetero oxygen and / or hot nitrogen atom according to point 3 f) of the main patent or are partially replaced by corresponding compounds with at least one further basic nitrogen atom in the molecule./V _t - 13 - 209824/0843 BATH Henkel & CIO GmbH Se »· \ '^ to patent application D 4O46 2. Enzyme preparations according to Claim 1, characterized in that they have a pH of 5-10. 3. Preparations according to claim 1 and 2, characterized in that that they contain proteases from Bacillus subtilis. 4. Preparations according to claim 1 to 3> characterized in that they are used as stabilizer component A 2a ethylene glycol, di-ethylene glycol, tri-ethylene glycol, 1,2- or 1,3-propylene glycol, 1,3- or 1, 4 ~ Contains butylene glycol or glycerine-CF monomethyl ether. 5 · Preparations according to claim 1 to 4, characterized in that that they are used as a stabilizer component 3 e) compounds from Type of i-cyclohexylamino-3-aminopropane, 1-aminomethyl ~ 2> aminocyclopentane, 1,2-propylenediamine, 1-dimethylamino or 1-diethylamino-propylamins-3> bis- (3-aminopropyl) -methy! amines, Diethylenetriamine, triethylenetetramine, tetraethylene pentamine or N-hydroxyethyl ethylenediamine and / or as stabilizer component 3 f) compounds of the type des Contain N-methylimidazole or 2-methylimidazole, 6. Preparations according to claim 1-5, characterized by a content of antimicrobial substances. 7. Preparations according to claims 1-6, characterized in that that they are 10 to 50 wt .-> i a combination of one part by weight of the polyhydric alcohols or their partial ethers according to claim 1 A2a and 1.5 to 5 parts by weight of the according to the invention Substances to be used instead of the stabilizer components according to point 3 e or 3 f of the main patent contain. - 14 -.- ι., 209824/0843 BATH Henkel A CiQ GmbH Ropes 1 4 for Potonlanmoldung D 4O46 8. Preparations according to claim 'J, characterized by a content of about 1 part by weight of carboxylic acids according to claim 1 A4. 9. Preparations according to claims 1-8 which can be used as detergents and cleaning agents, characterized in that they contain 0 to 25, preferably 1 to 15 weight; ' Surfactants and 0 to 25, preferably 0.5 to 25 wt .- # builder substances, especially inorganic ones or contain organic complexing agents. 10. Preparations according to claim 9, characterized in that the sum of surfactants and builders is 1 to 55 *, preferably 5 to 5 ° wt .- ^. 11. Preparations according to claim 1 - 10, characterized in that that they have 1 to 50, preferably 5 to 50 wt .- ·· -) of solvent contain.//, 209824/0843 BAD ORiGtNAL