DE1692016A1 - Enzymatic granular detergent and process for making same - Google Patents

Description

The invention relates to granular, non-segregating Detergents and cleaning agents with a content of enzymes » non-ionic synthetic washing active substances and inorganic ones Cleaning salts. The production of powdery, enzymatic detergents usually takes place in such a way that the spray-dried detergent mixtures the pure or blended with an extender or to an inert one Carrier substance applied enzymes are zugemiseht. The particle size distribution and specific weights of the voluminous spray powder and the enzymes or the enzyme-containing ones However, preparations usually differ from one another, so that the powder mixtures at. Filling, loading or at Transport L can segregate to a considerable extent.

Another major disadvantage is that of the dry mix of spraying powders and enzyme preparations. ^ι ι-; α'.ΐΐΙηοΛ \ ο is your opinion on dusting. The ho oh akb Lv on Cnzyrno practice a nui-torordwnt 1 i Oh.-s-LarkG ■

10903071.876. -P--

Irritant effect on the mucous membranes, which extend up to the Mucosal bleeding can increase. This unpleasant side effect is not only caused by those on the mixing devices, the filling plants and those involved in the transport Persons concerned, but also the consumer, who at ' Using the pack with the air that contains enzymes Picks up dust.

^ - Ss Attempts have therefore already been made to counteract the tendency to segregate and dust by using the spray-dried washing powder beforehand with liquid active substances sprayed or with crystal! Salts mixed, whereby the subsequently added enzymes are supposed to stick to the washing powder particles. A disadvantage of the enzyme-containing mixtures prepared in this way, however, is that the longer the storage tent increases there is a loss of enzyme activity. This is particularly true when the detergents contain anionic washing active substances

and per compounds contain or. longer time at increased It is imperative to store the air or at higher temperatures. As with the previously known methods, the loss of activity the enzymes were not or not significantly damaged can, one is content with the rlnzymmcinge in the production dos Viaachpulvers so far that after olnor average Lagorzo.it. α Luc still has no living effect .is.

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The disadvantages described are eliminated by the present invention avoided. The subject of the invention is a granular, Scatterable detergent with a content of anionic washing active substances, inorganic cleaning salts and per compounds, which is characterized in that it consists of a mixture consists of at least three powdery components, One component of which is the anionic washing active substances, a second the per compounds and a third, of anionic detergents Active washing substances and per-compounds free component, inorganic cleaning salts and, if necessary, organic complexing agents contains, the powder particles of the last-mentioned constituent being wholly or partially provided with a coating are essentially composed of a mixture of an enzyme with at least one nonionic detergent raw material from the class the polyglycol ether derivatives of alcohols, fatty acids and alkyl phenols, the 2 to 30 glycol ether groups and 8 to 20 carbon atoms contained in the hydrocarbon residue, as well as the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 Polyether-lenoxide adducts containing propylene glycol ether groups on polypropylene glycol, ethylene diamino polypropylene glycol and Alkyl polypropylene glycol having 1 to 10 carbon atoms in the Alkyl chain.

Suitable enzymes are those, for example, animal and vegetable Ursprungsy come from Verdatmngsfermenten, yeast, fungal and bacterial strains in question agents 4J ₁ recovered. they provide

^ mostly a complicated mixture of different

- * ■■ -, - ·. ■. -

** ner enzymafcischer active ingredients. Depending on their effect

^m know here as proteases, carbohydrases, esterases,

Oxidoreductases, catalases, peroxidases, ureases, isomerases, Desmolases or nucleases denotes; Of particular interest are those from bacterial strains of dull fungi, such as Bacillus subtilis and Streptomyces griseus enzymatic agents. VJeite.ro are suitable enzymes Pepsin, pancreatin, trypsin, papain and diastase. From The enzyme preparation obtained from Bacillus subtilis has the advantage over the latter enzymes that "." are relatively resistant to alkali, per-compounds and anionic washing active substances and also at temperatures not noticeably inactivated between 45 ° and 70 ° C will. Their relatively high resistance to oxidizing agents is possibly due to the low Free sulfhydryl group content.

The enzymes are made by the manufacturers, possibly with the addition of Extenders such as sodium sulfate, sodium chloride, alkali phosphates or alkali polyphosphates, adjusted to a certain level of activity. The information in LVE / g (Löhlein-Volhard units per gram), IE (international units) and DE / g (DeIfter units per. Gram) * In technology, the activity is often expressed in LVE / g. give as the analytical method of determination that this Key figure is based on, comparatively easy to implement is. In the detergents according to the invention, the

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Enzyme activity 100-5000, preferably 200-2000 LU / g be. The amount of enzymes to be used in detergents is also based on these values.

The nonionic polyglycol ether derivatives are by attachment from ethylene oxide to primary alcohols, fatty acids and alkylphenols as well as to polypropylene glycols and polypropylene, glycol derivatives available. Which contain alcohols and fatty acids preferably 12 to 18 carbon atoms and can be of natural or synthetic origin. The alkyl phenols are iron preferred straight-chain alkyl groups with 6 to 12 carbon atoms. Polyglycol ether derivatives of fatty alcohols and alkylphenols in which the number of ethylene glycol ether groups is particularly suitable 5 to 15.

By adding from 5 to 15 moles of propylene oxide to the latter Polyethylene glycol ether or by converting into the acetals are obtained by a detergent particularly low foaming properties.

In the preparation of the water-soluble reaction products of ethylene oxide with polypropylene glycols or polypropylene glycol derivatives, one starts from polypropylene glycols or from polypropylene oxide adducts with aliphatic alcohols having 1 to 10, preferably 2 to 6 carbon atoms, or from polypropylene oxide adducts with ethylene diamine Number of propylene glycol groups is 10 to t00. For conversion into water-soluble

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They are ethoxylated surface-active compounds, with those products of particular interest in which on a propylene glycol unit has 1 to 5 ethylene oxide units omitted.

The agents according to the invention should preferably total 0.05 to 5 * 0.1 to 2 wt .-? A of enzymes. Have yourself proven agents whose content of the enzyme-free, anionic detergent raw materials or per-compounds containing powder constituents 50 to 98% by weight, preferably 70 to 95% by weight and an the enzyme powder component 2 to 50 wt .- $, preferably Is 5 to 30 wt .- $.

The enzyme-containing powder component is composed of the powdery component containing the inorganic cleaning salts, which is referred to below as "pre-powder" and the coating agent, which consists essentially of enzyme and nonionic active substance. The coating agent expediently contains 50 to .95 wt. of nonionic washing raw materials and 5 to 60 wt .- ^ of enzymes. Enzyme contents lower than 5 % are also possible, but relatively large amounts of non-ionic washing raw materials have to be sprayed onto the pre-powder, which can lead to the powder sticking. It is advisable not to apply more than 50 parts by weight of coating agent to 50 parts by weight of pre-powder. The enzyme content of the coatings is therefore preferably 10 to 10% by weight.

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SAD ORiöiHM.

1892016

The pre-powder should have a bulk density of 200 to 900 g / l. Such powder compositions are in various V / else receives lent liquid for example by hot or Kaltversprühung v ^ on or pasty concentrates or by adding in by crystallization processes solidifying paste, a gas, for example · air is blown in finely divided form or gas-evolving substances are added As described, for example, in the German Aus lege writings 1 016 881 and 1 09I "263. Furthermore, powder mixtures produced by granulation or fluidization according to the fluidized bed process, optionally with simultaneous use of hot air, can be used.

The prepowders produced in the specified manner contain, as the main constituent, inorganic addition salts and, if appropriate, complexing agents or other non-ionic washing active substances. Examples of inorganic salts are Pentanatriuintriphosphat cleaning, pentapotassium triphosphate, or their mixtures, in quantities of 10 to 60, preferably 20 to 50 wt -.% May be present. The triphosphates mentioned can hydrolyze to a small extent to pyro- or orthophosphates during drying, so that these salts are mostly present in a mixture with the triphosphates.

In addition to the triphosphates, the prepowders can be more highly condensed Phosphates, such as tri- or polymetaphosphates, and silicates

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In the form of their alkali salts, as well as stabilizers such as magnesium silicates, contain. Complexing agents can also be present, in particular alkali metal salts of aminopolycarboxylic acids and / or aminopolyphosplionic acids, viie the sodium or "" Potash salts of aminotr! Acetic acid, ethylenediaminotetraacetic acid, Diethylenetriaminopentaes.sigsäure, triethylenetetraminohexaacetic acid and their higher homologues, Ä'thylenediaminohydroxyathantriess igs acid, aminotri- (raethylenephosphonic acid), Kthylendlarninotetra- (methylenephosphonic acid), 1-hydroxyethane-l, 1-diphosphonic acid and the higher homologues of the polyphosphonic acids mentioned.

The powder fraction containing the anionic detergent raw materials can Be prepared in the same way as the "pre-powders. Preferred are powder produced by spray drying with a bulk density of 200 to 500 g / l and a high content used on hollow spherical grains. In addition to anionic VJash raw materials, the above mentioned cleaning salts, stabilizers and complexing agents be included. Examples of anionic detergent raw materials are olefin sulfonates, such as, for example by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and then alkaline or acidic hydrolysis can be obtained, as well as alkylbenzenesulfonates, alkylsulfonates and e ^ -Sulf of enoic acid esters, also primary and secondary alkyl sulfonates and the sulfates

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• ORIGINAL BATHROOM

of ethoxylated or propoxylated alcohols. More connections of this class, which may possibly be present in the detergents, are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali salts of the monoalkyl ethers or the monofatty acid esters of Glycerol monosulfuric acid ester or 1,2-Dloxypropanesulfonsäure. There are also sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols and fatty acid taurides and fatty acid ethionates.

In addition to the sulfate and sulfate type washing raw materials mentioned, this powder fraction can also contain alkali soaps of fatty acids, ampholytes, viie alkyl betaines and alkyl sulfobetaines, as well as nonionic detergent substances such as alkyl and acyl polyglycol ethers, alkylphenol polyglycol ethers, mixed condensates of polyethylene glycols and fatty alcohols, as well as polyethylene glycols and polypropylene glycols . The washing active substances mentioned can also be present in a mixture. ■

If the detergent compounds mentioned are aliphatic Have hydrocarbon radical, this should be preferred be straight chain and have 8 to 22 carbon atoms.

- 10 -

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In the compounds with araliphatic hydrocarbon radicals contain the preferably unbranched alkyl chains "6 to 16 carbon atoms on average.

Foam stabilizers such as fatty acid mono- and dialkylene amides can also be present as components of the mixture. Agents intended for use in washing machines instead contain foam inhibitors, for example fatty acids or their alkali soaps with 20 to 2 ^J i carbon atoms or triazine derivatives, which are obtained by reacting 1 mole of cyanuric chloride with 2 to 5 moles of an aliphatic, straight-chain, branched or cyclic primary monoamines are available. Graying inhibitors such as sodium cellulose glycolate, disinfecting and finishing agents as well as dyes and fragrances can also be present.

The agents can also be used as compounds with bleaching agents Effect contain, such as perborates, percarbonates, perpyrophosphates, persilicates, persulfates, urea perhydrate and organic peracids or peroxides. Sodium perborate tetrahydrate is preferably used, in amounts of 5 to 55 * preferably 15 'to 50 cS by weight, based on the Total amount of detergent ingredient Gn, can be present.

In addition to a good dirt-loosening. Effect, especially for fat and protein containing impurities, at temperatures between -20 and 70 C. the enzymes also cause an activity

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Vierur} £ the in 6 or. ".. * a schnittein contained per compounds, so da5 their bleaching V / MPACT already at temperatures between 50 and JO C starts.

For the production; the gowns made in accordance with the invention are the 3hzyme in your liquid, possibly by heating or by low Addition of water to liquefied non-ionic ash raw materials suspended. The enzyme-containing suspension is at temperatures between 20 ° and 70 ° G, preferably between 50 and 50 C, the pre-powder sucemixed, with usual, continuous or discontinuous spraying or mixing devices can be used. A particularly even mixture can be achieved by spraying the suspension into a freely falling powder stream or by the suspension introduces or blows into this spray jet by means of a at the upper end of a vertical chute. More suitable Devices of the specified type are for example in German patents 459 8 ^ 2 and 602 996, also in the German Auslegeschriften 1 183 889, 1 196 859 and 1 197 064.

Mixtures of different nonionic raw materials and enzymes can also be used to produce the suspension. Furthermore, substances can also be dispersed in the suspensions which are usually added to the detergents only after spraying, since they are volatile or decomposable under the conditions of kiss atomization.

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. - 12 -

are partially inactivated, however, the effect of the enzymes not affect. These include fragrances and dyes, preservatives, organic silk, foam inhibitors, skin protection agents and deodorants.

The various powder components, i.e. the enzyme-containing pre-powder that contains the anionic detergent raw materials Powder and the sodium perborate are then mixed together, the mixing in one or more Operations, preferably continuously, carried out ^ - can be.

The agents according to the invention tend during filling and the transport does not lead to segregation. Their tendency to dust is very low. Even after a long period of storage none can be notice a significant decrease in enzyme activity. Another advantage of the agents according to the invention is therein too see that the enzymes are completely enveloped by the nonionic washing active substance, so that consumers too with sensitive skin without the risk of skin irritation Can remove and dose agents by hand. The funds are particularly suitable for use in fully automatic Washing machines, as they have a very good dispensing capacity, i.e. they dissolve without residue in a very short time.

The detergents according to the invention are characterized by a high cleaning power even in cold and moderately warm water

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from «They can also be used with advantage as a cooking detergent, wherein the enzyme during the heating of the wash liquor becomes fully effective. Means / which the mentioned sugary inhibitors are particularly suitable for washing in fully automatic Drum washing machines. Detergent compositions with a pH in aqueous "solution of 9 - H will be preferably used for washing cellulose fiber textiles « For washing delicate fabrics, especially those made of wool, silk, semi or fully synthetic fibers, neutral or slightly alkaline detergents are used.

The agents can also be used advantageously as soaking or pre-washing agents, the laundry either being left in the washing liquor for several hours at room temperature or being prewashed in it for 10 to 60 minutes at temperatures between J> 0 and 60 ° 0. The subsequent, to be carried out at temperatures between 70 and 100 ⁰ C hot wash is advantageously performed with the same wash liquor. A longer soak or pre-wash is particularly recommended when cleaning laundry soiled with protein.

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Example e

The composition of the detergents is shown in the table below. The powder with the constituents a to m was produced by spray-drying a pasty batch and had a bulk density of 320 g / l. On the powdery phosphates (components η and o). with a bulk density ^ ron 700 g / l of a suspension containing the ingredients was to t ^ sprayed ρ. Both powder components and the liatric perborate (component u) were then mixed with one another.

The foam dampening agents are reaction products of 1 mol of cyanuric chloride with 2.6 mol of a primary n-alkylamine of chain length Cq-C., q, where a mixture of Compounds of the following formula was obtained in which R denotes the alkyl radicals listed. represent;

RHÜ-C ^/ C ~ NHR R HN-C \ -NHR

i -ι ι l. _ ..

^. HN and N _v N

·% • \ ^y ■

HNR Cl

Commercially available enzymes were used in the Examples 1 to 4 the preparation Alkalase ^ from Novo Industri., Copenhagen * with an activity of LV £ 1,000 / g and in Examples 5 to 8 the preparation Maxatase ^ der

- * Koninkijke Nederlandsche Gist en Spiritusfabriek N.V.,

^ - Delft, with an activity of loo.ooo LVR / ß · the optical ω

Brightener consisted of a mixture of a diarninostilbene-visulfonic acid derivative and a diarylpyrazolind.crivatos

cn

co

^ in the ratio>: 1.

The abbreviation A'O means ethylene glycol groups.

BAD ORSQWAU

ο (D OO CO O op co ro '
>
ο O 33 Q

a) Na-n-dodecylbenzenesulfonate

^b >

(Na-SaIz)

^{C) C} i2 ' ^C ₁₈ " ^{Fet £ alcohol} ° l5Ulfat (Na-Salt)

d) Na soapC -C

12 18

e) Na soap C -C

2o 22

¹ P) CC -Feitalcohol polyglycol ether (10 AO) q) Nonylphenol polyglycol ether (9 AG)

r) enzyme

¹ s) foam suppressant

t) fragrance

U) sodium perborate tetrahydrate

V) water

Examples (information in Gevr, -%)

7.6 4.5

f) sodium silicate 2 g) Na cellulose glycolate 1.5 h) Na aminotriacetate . i) Na-ethylenediaminetetraacetate 0.5 k) optical brighteners 0.3 1) magnesium silicate 2 m) sodium sulfate, sodium chloride 2 n) pentasodium triphosphate 40 o) tetrasodium pyrophosphate 6th

3 1 1

0.3 1.6 1.6

45

5
2

10
10
0.4
2

1.5

25th

0.5

2.5

25th

0.5

2.5

16

4 4 2

3 3 1.5

0.3 2.1 2.5

25th 5

20th

1.5

0.5

2.3

0.5

-.16 -

Mixing took place in such a way that the enzyme-containing suspension, heated to kO to 45 ° C., was sprayed by means of a nozzle which was mounted in the upper part of an atomization chamber. The pre-powder was blown into the chamber at the same time through several concentric tubes arranged below the nozzle, so that the liquid and powder components were thoroughly mixed. The granules obtained were easily pourable, did not tend to clump or dust even after the other constituents had been mixed in, and were found to be extremely stable even under unfavorable climatic conditions.

In a further series of experiments, a suspension consisting of an enzyme alkalase with an activity of 14o, ooo LVE / g and a petroleum alcohol polyglycol ether or fragrances and dyes in a drum mixer on a spray-dried pre-powder consisting of pentasodium triphosphate and sodium aminotriacetate with a bulk density of 400 <g / l, sprayed on at a temperature of JO to 40 C. The received Granules had the following composition:

Components Examples (information Io 11 in parts by weight) 13th 14th 9 6th 6th 12th 5 6th enzyme 6th 20th 24 4th 15th 16 Ethoxylated oleyl alcohol (10 ÄO) 16 10 ' 0.2 - - dye - - 2.4 Fragrance - "69 65 - 79.8 75.6 Na-thiphosphate . 68 5 5 71 - - Na-aminotriacetate 10 15th

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BATH ORIGINAL

■ ■ - 17 -

Per one part by weight of the granules obtained was spray-dried with a ten Gewiohtsteilen s, pulverför ¹ - * "Raigen Waschmittelgemlsches following composition blended (bulk weight 350 g / l);

Sodium n-dodecylbenzene sulfate soap C ₁₂ -C ₁₈

Pentasodium triphosphate soda anhydrous ifetriurasilicate (Na ₂ OiSiO ₂ = I: 3.3 magnesium silicate ifatriumeeiluloseglycQlat optical brightener

In addition, 25 parts by weight of naphtha perboracite tetrahydrate were added zugeraischt »The washing powder contained the enzyme in a very even "distribution and did not tend to Dusting «The enzyme activity remained over a long period of time constant.

8th Weight .-Parts S. It Il 25th It H 15th Il Ii Il It 2, Il Il Il It O ₃ « It , 3 S. ΰΐ 3

bad original

Claims (1)

l) Granular, scatterable detergent with a content of anionic washing active substances, inorganic cleaning salts and per compounds, characterized in that it consists of a Geraisch of at least three powdery components, one component of which the anionic washing active substances, a second the per compounds and a third of Anionic washing active substances and per-compounds free component contains inorganic cleaning salts and possibly organic complexing agents, the powder particles of the last-mentioned component being wholly or partially provided with a coating that essentially consists of a mixture of an enzyme with at least one non-ionic washing raw material from the class of polyglycolate derivatives of alcohols, fatty acids, alkylphenols * which contain 2 to 50 glycol ether groups and S to 20 carbon atoms in the hydrocarbon residue, as well as the water-soluble * 20 to 250 ethylene glycol ether groups and 10 to 100 percent opylene glycol ether groups. containing lencöcicladdukfee on polypropylene glycol, glycol and ÄlkylpolyprOpylenslyaol MIFC ϊ to 10 Kohlenstoffatonien Iu the Älky! chain besteht- ·. 2} smock naeti. Claim 1, characterized in that it contains a total of 0.05 to 5% by weight of enzymes * _, ... 5} means naehx claim 1 and 2, daclurch gekennzeieiinefc that the proportion of the oinerit coating from non-organic washing active '.:.:. "<*> ,. 108830 / 1-8? Β ·· ■ * ■ - · -. ■■■ · _-. . " ₁₉ " .. - IAD ORIGINAL substance and enzyme-provided powder constituent 2 to G ew ..- £>, preferably 5 to 'j> 0 wt .- ^ f. 4) means according to claim 1 and 2, characterized in that that the coating 5 to βθ, preferably 10 to 40 wt .-; £ of enzymes. 5) means according to claim 1 to 4, characterized in that that the powder component provided with the coating has a bulk density of 200 to 900 g / l. 6) Means according to claim 1 to 5> characterized by a content of 5 to j> 5 wt% sodium perborate. 7) Process for the preparation of the means according to claim 1 to 6, characterized in that one consists essentially of inorganic cleaning salts and optionally organic complexing agents Mixes a suspension with existing powder with a bulk density of up to 900 g / l or part thereof, consisting essentially of an enzyme and at least one nonionic washing raw material from the class of polyglycol ether derivatives of alcohols, fatty acids and alky! phenols, the 2 to 30 glycol ether groups and 8 to 20 carbon atoms contained in the hydrocarbon residue, as well as the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to Polyethylene oxide additives containing propylene glycol ether groups - 20 - 1098 30/18 76 »AD ORIGINAL on polypropylene glycol, ethylene diamino polypropylene glycol and Alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain, whereupon the resulting ΡμΓν-er with other powdery, anionic active substances containing detergent ingredients and per compounds mixed. 8) The method according to claim 7 *, characterized in that a suspension is used which contains 5 to 60 wt. «$, Preferably 10 to 50 wt .- ^ enzyme. 9) Method according to claim 7 and 8, characterized in that that the suspension is sprayed onto the powder. 10) Method according to claim 7 *, characterized in that based on the final weight of the agent, 2 to 50 wt. * preferably 5 to 25 wt .- ^, that with the enzyme-containing sus Pension treated powder with further powdery, anionic detergent ingredients containing detergent ingredients and sodium perborate mixed. Henkel & Cie. GmbH. = · I.V. (Dr. Haas) (Dr. Kagel) 10 9 8 3 0/1876 OBlGlNAL