DE1811000A1 - Detergent containing enzyme and enzyme stabilizers - Google Patents

Description

LAWYERS

ALFRED HOEPPENER ^Ζ5 · Ν ™ 1968

DR. JMR. DiPL-CHFrM H.-J. WOLFP DR. JL ¹ R. HAMS-CoR. AX

023 FRANKFURT AM MAIN-HÖCHST

ADELONSTäASSEW

Our Ho. 15 202

The Procter and Gamble Company Cincinnati, Ohio, V.St.A.

Detergent containing enzyme and enzyme stabilizers

The invention relates to enzyme-containing detergents, in particular are suitable for removing dirt and stains from washed textile materials. In particular, it is around detergents that contain proteolytic enzymes and show increased enzyme resistance under unfavorable environmental conditions.

The use of enzymes in detergents is known. Compare with this US patent 1,882,279 from 1932 (Prelinghusen), British patent 814.772 from 1959 (Rohm & Haas GmbH) and East German patent 14.296 the year 1958 (Leidholdt), as well as the work of Jaag in "Seifen, Öle, Fette, Wachse" 88, Ho. 24, pages 789-793 (November 1962); enzyme-containing detergents are described in all of these publications. Although the mode of action of the enzymatic components in detergents in cleaning and removing stains is theo-

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retically cannot be fully explained, it can be assumed that the enzymatic components act as catalysts in the breakdown of Protein-containing dirt and protein-containing stains have an effect. But it has also been shown that the storage of enzyme-containing detergents Over long periods of time, especially in hot and humid climates, degradation and / or deactivation of the enzymatic Components can lead. The use of perborates as bleaching agents can also lead to a burden on the enzymatic Lead activity. The result of this dismantling and / or this deactivation is a significant loss of effectiveness in removing dirt and stains.

Numerous attempts have been made to improve enzyme resistance in detergents containing enzymes. A suitable method is for example in the Belgian patent specification No. 697,481. The manufacture of detergents., Which contain proteolytic enzymes and for long periods of time are resistant to high temperatures and high humidity, was at least partially made more difficult by the fact that the degradation and / or the deactivation of the enzymes leading reactions of the various components of the detergent with each other and were not completely clear with the enzymes. The invention enables the production of detergents with excellent dirt and dirt Stain removing power, in which the proteolytic contained therein Enzymes remain stable even after prolonged storage at high temperature and high humidity.

The detergents according to the invention can be in granular form and contain perborates as bleaching agents.

The invention relates to detergents containing proteolytic enzymes and are made up of the following components:

(1) about 60 to. about 98% of a mixture of an organic detergent raw material and an alkaline builder salt, whereby the

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ratio of. the latter is about 30: 1 to about 1: 4 " ;

(2) about 0.001 to about 2.0 $ of a proteolytic enzyme which exhibits its enzymatic activity in a pH range from about 5 to about 12 and at a temperature between about 10 and about 93 ^° C .;

(3) a partially hydrolyzed and solubilized collagen having an average molecular weight of at least about 5,000 in one for stabilizing the proteolytic enzymes sufficient amount.

The granular detergents containing proteolytic enzymes according to of the invention (in percent by weight, based on the total product) from about $ 60 to $ 98, preferably about $ 70 to $ 95, one Mixture of an organic washing raw material and a water-soluble one Builder salt. In the case of the organic washing raw materials that are suitable for the detergents according to the iCrfindung, it can be soap, anionic, nonionic, zwitterionic or ampholytic synthetic detergent raw materials or mixtures of these Act.

Examples of suitable detergent raw materials used according to the invention are the following:

(a) Water-soluble soaps - the sodium, potassium, ammonium and alkanolammonium (e.g. mono-, di- and triethanolammonium) salts of higher fatty acids ( ^ö - | o ~ ^ö 22 ^ are particularly suitable are the sodium and potassium salts of mixtures of fatty acids made from coconut oil and tallow, i.e. sodium and potassium tallow and coconut soaps.

(b) Anionic synthetic non-soap detergent raw materials - This class is generally water-soluble salts, especially the alkali metal salts, of organic sulfur reaction products, which in their molecular structure contain an alkyl radical with about 2 to 22 carbon atoms and a sulfone

9G9828 / 15A3

1011OQO

acid residue or a sulfuric acid ester residue. (The term alkyl here also includes the alkyl part of higher acyl radicals). DIq valuable examples of such anionic synthetic raw materials are sodium or potassium alkyl sulfates, in particular the products obtained by sulfating higher alcohols (Qq-O ^ q), which in turn arise from the reduction of the glyceride of tallow or eocoanut oil; Sodium or potassium alkylbenzenesulfonates in which the alkyl group is straight or branched and contains about 9 to 15 carbon atoms, preferably about 12 to 14 carbon atoms; Sodium alkyl glyceryl ether sulfonates, especially the ethers of higher alcohols derived from XaIg or coconut oil; Sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; Sodium or potassium salts of sulfuric acid esters of the reaction products of one mole of a higher fatty alcohol (for example tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; Sodium or Ealiumalkylphenol-iLfchylenoiydätheraulfate, which contain 1 to 10 ethylene oxide units per molecule and in which the alkyl radical has 8 to 12 carbon atoms; the reaction products of fatty acids are esterified with isethionic acid and neutralized with sodium hydroxide, the fatty acids being, for example, coconut oil; Sodium or potassium salts of fatty acid amides of a methyl tauride, in which the fatty acids come, for example, from coconut oil; Sodium and potassium salts of SO ₅ -buIfonierte O-jq-C ^ ^a "Ol & flaetL _t (0) Nonionic synthetic detergent raw materials - A class of non-ionic detergent raw materials is generally compounds that are formed by the condensation of alkylene oxide groups (which are more hydrophilic Kind are) with an organic hydrophobic compound; the latter can be an aliphatic or alkyl aromatic compound.The length of the hydrophilic olyoiyaifcylenrest, which is fused to any hydrophobic group, can be adjusted so that one is water-soluble Connection results, in the desired catfish an oleiohgewient between

dta hydrophilic and hydrophobtη elements consists. Bint widely Te KlMSt τοη nonionic vasohrohatofXea consists of higher jet acid amides. Bint third Kleist niohtioniaohe »¥ aeohrohstofie has seaipolar ligeneohaiten · Dies · drti EUestn can be further described in detail as follows»

(1) Sine Klagst von niohtioniiohen synthetic Vaiohrohetoffen is sold under the trade name ¹¹ PlUTOaIo ¹ *. These WasohrohetoXX connections are made by

Ethylene oxide condensed with tlttir hydrophobic bast, which duroh Kondtasatioa τοη propylene oxide has been obtained with propylene glycol. I) tr hydrophobic style dee molecules, the naiürlioh la Vaaaer is unlÖBlioh, has a molecularjewioht τοα approximately 1500 to 1800 on · The addition τοα Ροϊ »1 * & ΐ1 · α * ·· * β & an this hydrophobic style increases the water-solubility of the MoltkÜle as a goose, whereby the liquid character of the product is retained until the end of the spark. the polyoxyethylene content is about 5O ^ dta Oesajitgtwioh-fceB of the condensation product ob auaaaoht.

(2) Alkylphenol-Polyäthylenoiyd condensates are condensation products of Alky! Phenols, which in the alkyl group about 6 to 12 sole carbon atoms either have a straight or straight chain arrangement, with ethylene oxide, the ethylene oxide being in quantities of 5 to 25 per mole of alkylphenol toxhandea Compounds can be polymerized propylene, dubobutylene, ooten or honing,

(3) Nonionic synthetic VasohrohetoXXe can also condensation products τοα Äthylenoiyd with a product which obtained by the reaction of propylene oxide with ethylenediamine; such compounds contain about 40 to 80 (Jewiohtaprosent Polyoxyethylene and have a molecular weight between about 5,000 and 11,000. You connections are created through implementation of ethylene oxide with a hydrophobic base, which in turn

BADORiGlNAL

the r © »ktion8proaiAt au8 ethyleadiamine with üfeeraohüaaigea propylene oxide; the baae white thereby Vein Molelculargevfioht * ml sohen 2,500 and 3,000 au /.

(4) Other non-ionic Wasohrohatoffe include, for example ■ • cationic products made of aliphatic alcohols with 8 to 22 carbon atoms (straight or tera-branched chain) with ethyl aoxide, away. Coconut alcohol-ethylene oxide condensate, in which 5 30 Hol ithylenoiyd per hol of xoconut alcohol.

(5) The ammonium compounds, monoethanol and diethanolaides Fatty acids, the aoyl radical of which has about θ bit 18 carbon atoms, are also brewable nonionic Waachrohotofie. The Aoylreate slnd / lblioherweiee of naturally occurring (Jlyoeriden derived, e.g. from lokoanut oil, palm oil, soybean oil and tallow j the products can also be of eynthetieo origin • a and s.B, from the oxidation products of petroleum or the hydration products of the molybdenum oxide exist in the Flaoher-Tropsoh-Terfahren.

(6) Marine polar non-volatile Waaohrohatoffe aroundXassen long-chain tertiary amine oxides corresponding to the general formula

H ¹ - (OH ⁴ L - i

correspond, in which H ¹ eil ⁿ alkylreat with about 8 to 18 carbon atoms, R ² and B ^ each denote methyl, ethyl or hydroxyethyl, R ^ ethylene and η a number swlsohen 0 and about 10. Boron arrow in the formula indicates a βθ-alpolar bond in the usual way. Special examples of amino acid raw materials include simethyl oxydeoyl rinoxide and bi- (2-hydroethyl) dodecylaminoiyä,.

BATH ORIGINAL

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(7) Other semipolar nonionic detergent raw materials are long-chain tertiary phosphine oxides which ^{correspond to the formula RR'R M} P-> 0, in which R is alkyl, alkenyl ^{or monohydroxyalkyl with 10 to 20 carbon atoms and R 1} and R ^{11 are} each alkyl or monohydroxyalkyl with 1 to 3 carbon atoms. In this formula, too, the presence of a semipolar bond is indicated by the arrow. Examples of suitable phosphin oxy de are described in US Pat. No. 3,304,263, and may be the following: Dimethyldodeoylphosphine oxide and dimethyl (2-hyäroxydo <5eoyl) phosphine oxide.

(8) Yet another group of semipolar nonionic synthetic vasoharbons comprises long-chain sulfoxides formula

in which R ^ is an alkyl radical having from about 10 to about 28 carbon atoms, 0 to about 5 ether bonds and 0 to about 2 hydroxyl substituents, with at least one £ R ^ part Is alkyl radical without ither bonds, which contains about 10 to 18 carbon atoms. Furthermore, in the formula, R denotes a Alkyl radical with 1 to 3 carbon atoms and 1 to 2 hydroxyl groups. Specific examples of such sulfoxides are: Dodecylmethyl sulfoxide and 3-hydroxytrideoylmethyl sulfoxide.

(d) Amopholytic synthetic detergents can generally be used as derivatives of aliphatic / secondary and tertiary Amines are described in which the aliphatic radical consists of straight-chain or branched-chain alkyl groups can and in which one of the aliphatic substituents contains about 8 to 18 carbon atoms and also contains an anionic water-solubilizing group, e.g. Carboxy, SuIfο, Has sulfatο, phosphates or phosphoao. Examples of such compounds are Iatriua-3-ilodecylaminopropionate and Sodium 3- (3o (Jeoylaminopropaneulfoiiat.

ORIGINAL INSPECTED

(e) ZwitterioniBohe synthetic Waschrohetoffe can generally ale derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatisohe radical may be a straight or comparable _r zwelgtkettige alkyl group and in which one of the aliphatic Subetituenten about 8 to 24 Contains carbon atoms and also has an anionic water-solubilizing group of the type already mentioned "Examples of compounds of this type are 3- (IT" 1i-dimethyl-N-hexaäecylammoniö) propane-1-sulfonate and 3- (IT, li * -Dimethyi -lihexadecylammonio) -2-hydroxypropane-l-sulfonati such detergents are used because of their favorable behavior when washing in cold water. TgI * the Canadian patent specification 708.148.

The preferred organic washing raw materials used are it is sodium alkylbenzenesulfonate, Katrlumalkylsulfat and mixtures of these substances in which the alkyl group is straight-chain or branched chain and contains from about 10 to 18 carbon atoms. Specific examples of particularly suitable organic Raw materials are sodium deeylbenzenesulfonate * sodium dodecylbenzenesulfonate, Sodium tridecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, Sodium hexadecylbenzenesulfonate, sodium octadecylsulfate and sodium tetradecyl sulfate.

Piping soaps and anionic, non-ionic, ampholytic and zwitterionic non-soap detergent raw materials can be used alone calibrated or mixed with each other. You can also used in connection with other well-known Waeehrohstoffe will.

Bie alkaline Gerüetetoff ealz ·, a ie in d 'n Waechmittela gtmäß the invention can be eiageeetzt be used in solohen quantities dal "I have a weight ratio of alkalieöhea Öerttetstöffsal * au orgaaieöhem Wasöhrohstoff of about 30j1 to 1> 4, vorzugeweise about 15 * 1 to about 1r1 results. These builder salts

θ 0 9 8 28/1543

OfWGlNÄL IMSPEGTED

(οι α < 'θ #

(^. 0 0 Ov 0 0 0

■ I ■ ■ ι: CCI · t 1>f; 0

• ίο ί -c ν 0

I ■■ ι [(I Γ;

α c α C c ■ '■ ro

can be selected from the largest number of ctoppe and sub-tabs. Qeeigatle alkalieoht anorgaaiioht GerUetetofiaalae Bind bslapielawelae alkali metal carbona-be _t -pboipnate, -polyphOip ^ a-fe and -iilikat ·. Speiif high contents for "olcht Öalie elnd iatrium- and laliuaitripoiyphoiphat ·, -oarbonatt, -paoephat · and

Suitable oiffaaiaohe Oeartli ^ etoffialae uafaiieü Ammonium- and euie-substituted AantQQiuMii ^ lyiheepttjittaie ^ -polyacetate

ι be special the 'falrium- ' ^ | j | l) LuMealie, ₍ f ^ | _:

. ** ^ i ^ il ^^ Hi ^

how further; ^ S * | ie (| i ^ ii ||| j ^^^ -. ^ - LAa *** - * -.

^! | P | f | .ee:, ^, iff ^ ii., «» Ifif den auealoMahang ϋβηο ·

turn around

1-njlroiy- and itnan-a-hydroxy-iti ^ -iripfeoephonettuqfe, propane-1 »11 ■ 3 * 3-» l3t «> pan-1, t, 2» 5- and propanr-1 ₁ 2 »2i

Btlaplele for the Polyphoephonteitlndungen mentioned above and in U.S. Patent Nos. 3,159,581 and 3,213,030 and In the Belgian patents 672.209t 691.788 i »4 712.773 called ·

Polyacetate oils suitable for Xweokeder irflndung; Bind lie latriu »-, Kai ium-j Lithium, Amoniuil Utt # substituted JünmoniuMealae of the following acids: Ithylendlamintetraessig8äur * _r Ii- (2-HydroxyIthyl) -äthylenediaaintrie8eigeäure _f N- (2-Hydroiyäthyl) -nitrilodibhentrigeic acid, dietetic one Diaminocyoloheiantetraeesigaäure and Nitrilotrieeigeäure, The trisodium ala · of the above acids are generally used with preference. .

0098 2 8/1543 ORIGINAL INSPECTED

Si · folyoartooxylat ~ 0erttatetoffaalse _t which can be used for the purposes of the discovery »consist of water-soluble salts of polymeric aliphatic polycarboxylic acids, whereby ea« s are compounds of the following groups

(e) wesserlusliche Selie von Homopolymetfea γοα allphatiecb-?) Polyoartjonatturea of the tepirieofein Iomeli

13th - 4 - 0.

i iooH

in which X, T and Z are Vasaereteff, methyl, carboxyl or oxymethyl and at least one of the radicals X »Y and Z ede * are arboxymethyl - under the gate setting _t dad X ind 7 only mean küitt ·» »if SS is carboxyl or oarboxymethyl represents - only one l®r X, may be I and% methyl and a is a gait "· ZwMl is within a range" whose lower fetus' $ uni whose upper bridle from the Ijöslichkeitssigensohaften in a wKirigen system results ι

(B) water-soluble salts τοη misoh polymers from at least siwei Types of honors that follow the empirical formula given under (a) to give is to correspond!

(o) Water-soluble salts of copolymers τοη alkylenes and monocarboxylic acids with the aliphatic polyoarboxylic acids mentioned under (a), did the formula
. 4 - 4 Λ ( - 4 - b - Λ ^ k ί J Ii horn)

(1-m)

eatepreohen, la which R is hydrogen, methyl, carboxyl, Oarooxymethyl or OarDOxyäthyl represents, but only a B group methyl β β in lc can; m at least 45 percent des interpolymer means; X, Y and Z hydrogen, methyl,

909628/1543

Carboxyl or Oarboxymethyl and at least one of the groups I » Y uad Z mean carboxyl or oxymethyl, but with the proviso that Z and T can only be carboxymethyl when Z is carboxyl or carboxymethyl; only one of the groups X, I or Z can be methyl and η is an integer a Bereioh, whose lower (bridle is at 3 and whose upper limit mainly due to the beneficial properties established in an aqueous system 1st. This polyelectrolyte armor material has a minimum molecular weight of 350, calculated on the acid form, and an equivalent fled from about 50 to 80, also calculated on the acid form (e.g. polymers of itaoonic acid, aoonitic acid, maleic acid, mesaconic acid, fumaric acid, methylenemalonic acid and cltraonic acid, as well as Homopolymers of these acids with one another and with other compatible monomers such as s »B. ethylene). These carboxylate beneficial agent salts are particularly described in U.S. Patent No. 3,308,067.

Mixtures of the aforementioned Gto make-up salts can also be used * -part can be used for the purposes of the invention.

The proteolytic enzymes which are useful for the purposes of the invention are enzyme-related materials which can generally be classified in a known manner as alkaline / neutral and acidic proteases. The designation alkaline proteases, neutral proteases and acidic proteases occurs with regard to the pH range in which the proteolytic enzymes develop their highest effect in the enzymatic cleaning. Door are the Zweoke the invention suitable proteolytieohe Eneyme products rlsοhen your enzymatically · activity in the pH Bereloh "about 5 and about 12 and swlsohen at temperatures about 10 and about 93 ⁰ O unfold. In this context, the proteolytic activity is understood to mean the ability of a proteolytic enzyme to perform the desired function of catalytic change or catalytic degradation of protein-containing dirt or protein-containing pools. Under Consistent

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ORIGINAL INSPECTED

The ability of the proteolytic enzymes to maintain their enzymatic activity.

Although the exact mode of action of the proteolytic enzymes in cleaning and stain removal has not yet been fully clarified it can be assumed that the reaction mechanism involves hydrolysis of the peptide bonds of proteins, polypeptides and related compounds present in dirt and stains, leading to the formation of free amino and carboxyl groups and long-chain protein structures are broken down into shorter chains - the latter can be extracted from the tissues with the help of aqueous solutions of organic detergent compounds removed.

Specific examples of proteases which are useful for the purposes of the invention are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, the subtilisins, papain, ficin, bromelin, carboxypeptidase, aminopeptidase and aspergillopeptidase A and B, as well as the proteolytic enzymes, which are isolated from the Streptomyces species, for example Streptomyces Griseus. The proteolytic enzymes preferred for the purposes of the invention are the subtilisins which are obtained from the bacterial organism Bacillus subtilis, for example Carlsberg and BPN 'strains, and proteases which are isolated from Streptomyces species. The amino acid sequences of Carlsberg subtilisin and BPN'-subtilisin are described in Smith et al., "The Complete Amino Acid Sequence of Two Types of Subtilisin, BPF ¹ and Carlsberg", J. of Biol. Chem., Vol. 241, 25 . December 1966, page 5974th another particularly suitable proteolytic enzyme is obtained by Anthrobacter bacteria and buys be obtained from the company Aktiebolaget Astra, Södertälje, Sweden, the protease is described in US Patent 3,345,269. ³

The proteases described above can be used in their pure form for the production of enzyme-containing detergents. In general but if you use the powdered commercial enzyme

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products that contain the enzymes mentioned. These commercial products contain from about 2 to about 80 $ proteolytic enzymes in combination with inert powdery carrier or filler materials, which can consist of sodium or calcium sulfate; the latter are $ 20 to $ 98 each. These commercially available Products can also contain smaller amounts of fat and carbohydrate materials as well as lipaae or α-amyis. Lipase Among other things, products are desired and can support the cleaning process. Specific examples of these commercial products and their manufacturers are: Alcalee, Novo Industri, Copenhagen, Denmark; Maxatase, Koninklijke Nederlandsche Gist - En Spirltusfabriek N.V., Delft, Netherlands; Protease B-4-000, Sandoz AP and AP 2100, Sandoz, Basel, Switzerland; CRD protease, Monsanto Company, St. Louis, Missouri; Pronase-E, Pronase-P, Pronase-AS, and Pronase-AF, all from. from Kaken Chemical Company, Japan; Bioprase, Nagase 4 Co., Ltd., Osaka, Japan; Rapidase 400, Rapidase, Seolin, France; Hl proteolytic enzyme 200 and proteolytic enzyme 7ZB, Miles Chemical Company, Elkhart, Indiana; P-II concentrate, Rhozym PF, phthozym J-25, Rohm & Haas, Philadelphia, Pennsylvania; Wallerstein 627-P, Wallerstein Company, Staten Island, New York.

Pronase '• Ρ, Pronase-AS, Pronase-AF are produced by Streptomycea Griseus, and Alcalase and CRD Protease are produced by Bacillus Subtilis won.

As I said earlier, the amount of proteolytisohem Enzyme in the enzyme-containing ingredients according to the invention, for example 0.001 to about $ 2, preferably about 0.01 to about 0.53 * (based on on the whole and counted as pure Bnsya). The amount must be naoh for a specific detergent in each individual case the desired strength of the proteolytic effect and the degree of activity of the enzyme-containing product used.

If an enzyme product is used in which the active protease only in a small amount, e.g. about $ 2, available let and wel-

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As a result, if the activity level is in the lower range, a balance can be achieved by using a relatively large amount of this enzyme product.

Products that have a high proportion, e.g. 905ε, of proteolytic Containing enzymes can be used in a corresponding manner in smaller amounts.

The protein-like materials, of which it has now surprisingly been found that they have a stabilizing effect on the proteolytic enzymes in detergents, are protein substances obtained from collagen with average molecular weights between about 5,000 and about 250,000. Suitable proteins of this type can be obtained, for example, by partial hydrolysis of collagen. The partially hydrated and partially solubilized collagen proteins used according to the invention are obtained by partial hydrolysis or digestive breakdown of collagen with water, acid, alkali, heat, pressure, etc., whereby the conditions must be chosen so that the collagen is in water at room temperature (approx. 25 ⁰ C) becomes soluble or dispersible without the essential protein structure of the collagen being destroyed.

The partially hydrolyzed and solubilized proteins that can be used for the purposes of the digestive hydrolysis of collagen, which is present in a large number of naturally occurring substances, can be obtained. Collagen consists of high molecular weight, strongly cross-linked protein molecules and is found, for example, in the white fibrous connective tissues of mammals and fish as well as in the main tissues like skin, tendons and bones. Examples of starting materials containing collagen are sap hides, tanner waste (EaIb s skin θ, the are not workable on leather) and oasoin, (that is a material ^ that is obtained from dried animal knots and in which Acid treatment of the bones for the removal of the Calolunphosphates ■ urüok stays). These collagen-containing waste materials are

90982 8/1643

pre-treated in a usual manner to fat, mineral material and other protein as collagen to remove, and are then digested in the manner described above by the collagen is hydrolyzed by successive extractions of water at temperatures between about 49 and 100 ⁰ C. The protein-like collagen molecules are broken down by the successive hydrolysis stages, so that partially broken down collagen molecules are obtained which still have the amino acid composition of collagen, but have changed in molecular weight and in the swelling properties. Through the successive hydrolysis stages, the collagen material is broken down into protein molecules with constantly decreasing molecular weight and constantly increasing solubility. The even higher molecular protein molecules are swellable in water and are generally referred to as gelatin; they arise in the first stages of hydrolysis. Non-swellable protein materials of lower molecular weights and higher solubility, but which still have the characteristic amino acid distribution of collagen, are obtained in the following stages of hydrolytic degradation. Partially hydrolyzed and solubilized collagen proteins are those which still have the characteristic amino acid composition of collagen and have an average molecular weight of at least 5,000. Proteins that are completely hydrolyzed - which is to be understood to mean that the partial hydrolysis has been driven to such an extent that molecular weights below about 5,000 result - are for the

Purposes of the invention not useful. Partially hydrolyzed and solubilized proteins, which can serve to stabilize proteolytic enzymes, should have average molecular weights between about 5,000 and about 250,000. The hydrolyzed protein materials which are used according to the invention can also contain protein molecules below and / or above the specified ranges; the ranges given are average molecular weights.

Collagens, which are useful stabilizers for hydrolysis proteolytic enzymes are from Veis (Ed.) in Macromole-

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cular Chemistry of Gelatin, (1964) pp. 1-43. The conversion of collagen into gelatin is described by Kramer "Gelatin-How It's Made ", Food Engineering (November 1967) pages 75-77 and Veis (Ed.) I.e., pages 127-218. The other Degradation of gelatin to non-swellable collagen proteins has also been described by Veis (Ed.), I.e., pages 223-264.

All types of gelatins obtainable in this way, the average molecular weights between about 5,000 and about 250,000, as well as partially solubilized and hydrolyzed non-swellable collagen proteins with average molecular weights between 5,000 and 50,000 are useful for the purposes of the invention because drift stabilize the proteases used according to the invention. Particularly It is advantageous to use collagen proteins (namely swellable and non-swellable) whose molecular weights are between about 5,000 and about 100,000 are. Products with average molecular weights between 5,000 and 25,000 are even more suitable.

The collagen proteins used according to the invention are in general obtained in powder form and used directly in this form. It is important that these proteins be soluble or in water are dispersible. These properties, i.e. the solubility or Dispersibility, facilitate intimate contact of protease and protein - which will be discussed in more detail below - and reduce the deposition of proteins on washed fabrics, thereby reducing the build-up of proteins in turn, the tendency of the fabric to yellow as a result of this deposition is reduced.

Typical examples of commercially available collagen proteins are as follows Products: WSP-X-1000 (average molecular weight 10,000) manufactured by Wilson Chemical Specialties Co .; Knox gelatin (average molecular weight from 50,000 to 70,000) from Kind & Knox Co. and Swift Technical Protein Colloid # "I-V (Average molecular weight about 10,000) manufactured by Swift & Co. Collagen Protein is available in many commercial sources from many average molecular weights between. 5,000 and 250,000

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available. All of these collagen proteins can be used for the purposes of the invention.

The collagen proteins described above must be used in sufficient quantities to stabilize the proteolytic enzymes. Generally one uses the protein in such a Amount that a weight ratio of protein to pure protease of about 100: 1 to about 1:10, preferably about 20: 1 to results in about 1: 1. ♦

Without being bound to a specific theory, believed that the proteins described above preserve the enzymatic activity of the proteolytic enzymes by prevent the degradation, denaturation, autolysis and / or oxidation of the enzymes. It is further assumed that the mining, autolysis and denaturing oxidation are reduced by the presence of the proteolytic enzyme and protein in intimate association. The enzyme which is in intimate contact with the protective Biweißsjiubstanz is against the sohädliohen Influences of temperature, humidity and perborate bleaching agents and thus protected against degradation, denaturation, etc.

In addition to the washing raw material, the builder salt, the proteolytic A detergent according to the invention can also contain other enzymes and the partially hydrolyzed and solubilized collagen protein Additional common types and extenders included. For example, perfumes, anti-clouding agents, inert salts such as sodium sulfate, agents that prevent the redeposition of dirt, bacteriostatic agents, dyes, fluorescent dyes, foam stabilizers, anti-foaming agents, etc. tensile; sets his.

In a preferred embodiment of the invention, sodium perborate totrahydrate or sodium perborate monohydrate is added as a bleaching agent to the detergents. So far it has been assumed that by using sodium perborate in detergents containing enzymes

Θ09828 / 1543

decomposition of the enzyme occurs. On this, see Leidholdt, East German Patent 14,296. With the aid of the invention, however, stabilization can even be achieved in the presence of sodium perborate reach the protease. About 0 to 30 weight percent, preferably 5 to 25 weight percent, sodium perborate, e.g. Use in detergents in the form of monohydrate or tetrahydrate.

In a further preferred embodiment of the invention contains the detergent also has an acidic component, e.g. dihydrogendisodium pyrophosphate, Sodium bisulfate, sodium bicarbonate or mixtures of these substances; this also results an enzyme stabilizing effect «Preferably one uses the acidic component in conjunction with a builder salt and, if necessary, an organic detergent raw material as a carrier material for the proteolytic enzyme.

The enzyme-containing detergents according to the invention can be produced in any known manner. For example, a mixture of an organic detergent raw material and a builder salt can be used, which is in the form of spray-dried or agglomerated granules with a moisture content below about 8 $; you can also use a mechanical mixture of a granular organic Wasohrohstoffes and a builder salt. The granules of detergent or raw material may be of a size that about $ 100 will pass through a 6 Maeohen-Tyler test screen (3.33mm) and about 100ji will remain on a 200 mesh Tyler test screen (0.074mm). The separation or settling of the granules in the detergent decreases as the particle size distribution is further narrowed so that the granules pass about $ 100 on a 12 Maachen-Tyler test sieve (1.40 mm) and about $ 100 on a 100 Mesh Tyler test sieves (0.15 mm) remain. In order to prevent settling, the bulk density of the detergent granules should generally be between about 0.2 g / cm ⁵ and about 0.8 g / omr.

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Jn

The mixture of washing raw material and builder salt can be made soluble with the proteolytic enzyme and the partially hydrolyzed ^ Collagen protein are mechanically combined, so that a detergent results, which is excellent for cleaning and stain removal is suitable.

Preferably the proteolytic enzyme and the collagen protein should be used are in intimate contact in the detergents according to the invention. The üÄizym and the collagen protein can for example can be processed with water into a slurry or solution, which is then based on one or more granular components that make up composing the detergent according to the invention, are sprayed on. In this way, enzyme-containing granules are obtained which can then be mixed with the remaining detergent granules, which have been prepared in the usual way, are mixed. This is how you get the finished one detergents containing enzymes. The mixture of proteolytic enzyme and collagen protein should be combined with as much water as that there is a weight ratio of water / water to enzyme-protein mixture results in from about 1: 2 to about 4: 1. The granules that are sprayed can - as mentioned above - salt from alkaline builders, e.g. sodium tripolyphosphate or a mixture of organic There are detergent raw materials and alkaline builder salts. The proteolytic enzyme and the collagen protein can also be brought into intimate contact in another way, e.g. by agglomerating the enzyme and the collagen protein with a glue-like one Material, e.g. a liquefied non-ionic washing raw material.

So that the activity of the proteolytic enzymes is fully preserved, even in hot and humid climates, it is preferred to prepare enzyme-containing granules which contain the proteolytic enzyme, an acidic one Component and the collagen protein contain, produce and mix these enzyme-containing granules with detergent granules that are commonly used Way have been made.

909828/1543

An enzyme-containing detergent of this preferred type is best made by adding from about 80 to about 98 percent by weight conventional detergent granules containing from about 2 to about 20%, preferably from about 2 to about 12 percent by weight enzyme-containing granules mixed. A detergent according to the invention preferably has the following composition, for example: ($ = weight percent)

(a) about $ 80 to $ 98 of a blend of an organic laundry base and an alkaline builder salt in the ratio of the latter to the former of about 30: 1 to about 1: 4 »

(b) about 2 to about 20% enzyme-containing granules which are in saturated aqueous solution have a pH value between approx. 5 and approx. 8 and which (in percent by weight) consist of:

1) about $ 30 to about $ 75 of the builder salts already mentioned;

2) about 5 to about 50 $ of an acidic component in which

it is dihyrogenic disodium pyrophosphate, sodium bisulfate, May act as sodium bicarbonate or mixtures of these substances;

3) $ 0 to about $ 20 of a synthetic organic waso raw material of the type described above;

4) about 0.01 to about 50 $ of a proteolytic enzyme, whose enzymatic activity ^ unfolds in the pH range of about 5 to about 12 and at temperatures between about 10 and about 93 ⁰ G;

5) partially hydrolyze about 0.5 to about 20 $ of one and partially solubilized Oollagen, which serves to stabilize the proteolytic enzyme and an average Has a molecular weight of at least 5,000.

The main amount of detergents according to the invention, i.e. about 80 to · about 98 percent by weight, consist of detergent granules in an aqueous solution at a concentration of 0.12 percent by weight (usual washing concentration) have a pH of about 8.5 to about 11. This pH range has become more common for most laundry

90 9 * 8 28/1543

Twists found to be most effective under normal conditions. The detergent granules consist of alkaline builder salts and organic washing raw materials, the ratio of alkaline builder salts to organic washing raw materials between about 30: 1 and about 1: 4, preferably about 15: 1 and about 1: 1.

You remaining 2 to 2Ο $ ί, preferably 2 to 12 #, of the granular detergents according to the invention consist of the enzyme-containing granules. These enzyme-containing granules result in saturated aqueous Solution has a pH between about 5.0 and about 8.0.

The enzyme-containing granules are produced in a special way, so that they are of the same size and density as the detergent granules present in a predominant amount; to this This prevents the enzyme-containing granules from settling in the packaged detergents. Preferably the granules contain sodium tripolyphosphate and disodium dihydrogen pyrophosphate. The remaining components of the enzyme-containing granules Bind are selected so that they do not reduce the effect of the detergent granules and the detergent as a whole.

The grains containing acidified proteolytic enzymes, that have been sprayed with an aqueous mixture of enzyme and collagen protein can also be a simple misohung of the dry components, an agglomerated mixture or a spray-dried misohung leg.

to maintain optimal environmental conditions and maximum persistence of proteolytic enzymes in the granular To achieve detergent, it is beneficial to use moisture-proof packaging for the detergent. Moisture-resistant packaging is, for example, foil-covered cardboard boxes, asphalt-laminated cardboard boxes with Waohs on the outside - Cardboard boxes and polyethylene bags Further protection against unfavorable environmental conditions can be achieved if the washing agents according to the invention are also used, if necessary

909128/1543

ITodium perborate trihydrate, anhydrous trisodium phosphate, anhydrous Calcium sulfate or mixtures of these substances are mixed in. Even when stored in packs that are not moisture-resistant, the detergents according to the invention retain their enzymatic properties Effectiveness over a longer period of time than those containing enzymes Laundry detergents that do not contain collagen protein.

The following examples serve to further illustrate the invention.

example 1

Spray-dried detergent granules were made from the following components:

Component parts by weight 24.0 Sodium alkylbenzenesulfonate
made of tetrapropylene 18.6 Sodium tripolyphosphate 5.4 Sodium silicate (SiO ₂ : Na ₂ O in the ratio
from 2: 1) 24.3 Sodium sulfate 2.5 Sodium toluene sulfonate 6.2 water 2.0 Various (perfume, brightener, sodium
carboxymethyloelluloee) 83.0 all in all

10 parts of powdered sodium perborate tetrahydrate became uniform mixed with the spray-dried detergent granules obtained above. The detergent obtained was made up of parts with sizes between 3.33 mm and 0.074 mm and had a density of about 0.5 g / cm-.

A slurry that reads 1.00 part water, 0.53 part Λ1 ca (dleaesjf product contains 8 # active alkaline Oarlsberg subtilies and the rest consists of inert materials such as sodium and

909828/1543

Calcium sulfate) and 0.35 part / WSP-X-1000 protein (a powdered collagen protein which does not swell and has an average molecular weight of about 10,000) was prepared. This slurry was sprayed onto 5 _f 10 parts of granular anhydrous sodium tripolyphosphate, whereupon the protease-containing granules were uniformly mixed with the above-described mixture of spray-dried detergent granules and powdered sodium perborate.

This detergent was verpafct in Polyäthylenbeuteln and stored for 3 months under constant conditions of 32.2 ⁰ C and 80 $ relative humidity. The activity of the proteolytic enzyme was determined at specific intervals by the Azoooll method and compared with that of an enzyme-containing control detergent which had been prepared in the same way without WSP-X-1000 protein. The results are given in Table I.

noted
Per teaset Tabel I. Composition of the product
according to example 1 ^c fo remaining
Protease activity 0.72 noted
Amount of protease 100 Control product 0.63 i » lead
active protein
aseactivity 0.73 90 Days 0.56 100 0.66 94 0 0.41 87.5 0.69 85 24 0.28 78 0.62 95 51 57 0.69 93 39 123

The Azocoll analysis is based on the release of a water-soluble dye from a water-insoluble protein substrate (Azocoll) by a proteolytic enzyme. The amount of dye released under carefully controlled conditions is measured spectrophotometrically. The protease activity is calculated according to the amount of dye released. Usual anlytische variations are seen from Table I.

909828/1543

The results in Table I show that the enzyme-containing detergent according to Example 1 its enzymatic ^ activity with only little Protease degradation under unfavorable storage conditions maintained for a period of 123 days and in the presence of a perborate bleach. The control product suffered in the same Period of time a decrease in protease activity of $ 60.

The excellent resistance, which can be seen from Table 1, was confirmed by washing tests, in which test lobes with two different types of stains were used. The spots were egg spots and spots from EMPA 112 (Blood, milk and dye mixture). EMPA 112 samples were from of the Swiss Federal Materia ^ testing and research institute for industry, construction and commerce in St. Gallen, Switzerland. The detergents used to wash the samples were the control sample (no protein) and the product according to Example 1, both after storage under the same conditions of 123 days. The washed samples were assessed on a scale from 0 to 100, in which O the detergent effect of a detergent without protease activity and 100 the detergent effect of a freshly prepared protease-containing detergent means. The average rating of the control product was about 25; for the product according to Example 1 resulted average rating of about 75.

Example 2

Spray-dried granules of the following composition were produced!
Part by weight

Sodium AlkyTbenaisulfonate

made of tetrapropylene 24.0

Sodium tripolyphosphate 18.6

Hatri / iimailikat (Si0 _P ; Ha ₉ 0 in the ratio

from 2: 1 5.4

BatriuxsulifVfc 24.3

9 0 3 S 2 8/1 5 4 3

Sodium toluenesulfonate 2.5

Water 6.2

Miscellaneous (perfume, brightener, sodium carboxymethyl cellulose) 0.6

total of 81.6

10 parts of powdery sodium perborate tetrahydrate were uniformly mixed into the spray-dried detergent granules thus obtained.

5.25 parts of granular, anhydrous sodium tripolyphosphate and 1.40 parts of granular, anhydrous disodium dihydrogen pyrophosphate were dry-mixed and used as a carrier material for a proteolytic enzyme. The pH of these support materials is in aqueous solution at 7 _t. 7

A slurry containing 0.5 parts of Alcalase ($ 8 Carlsberg-Subtillsin, Remainder as already explained), 0.17 part of WSP-X-1000 protein (properties as described in Example 1) and 1.05 part of water was prepared and sprayed onto the dry mixture of sodium tripolyphaphate and disodium dihydrogen pyrophosphate. This mixture containing the proteolytic enzyme was uniformly mixed with the mixture of spray-dried detergent granules and powdered sodium perborate mixed.

A control detergent was prepared which had the same composition as described above, but with except that no WSP-X-1000 protein and no disodium dihydrogen pyrophosphate was included.

Parts of the control detergent and parts of the product according to Example 2 were packed separately in polyethylene bags and simple cardboard boxes. The polyethylene bag with the detergents were! Stored relative at 32.2 ⁰ C and 80 $ moisture 90 days. At the end of the period, the product according to the invention had approximately retained its initial protease activity

909828/154 3

Control product without protein and disodium hydrogen pyrophosphate had only retained $ 55 of its original protease activity. The combination of disodium dihydrogen pyrophoephate and collagen protein thus has an excellent enzyme stabilizing effect in granular detergents containing proteolytic enzymes. That The result of storage in simple cardboard boxes after 20 days of storage was as follows: The product according to Example 2 was 70% The initial activity of the proteolytic enzyme was retained, while the control product only retained 17% of the original activity of the proteolytic Had retained the enzyme.

Example 3

Spray-dried detergent granules with the following composition have been produced:

Component parts by weight

Sodium alkylbenzenesulfonate

Made from tetrapropylene 24 »O

Sodium tripolyphosphate 18.6

Sodium silicate (SiO ₀ : Na _o 0 in the ratio of

2: 1) ^{ά ά} . 5.4

Sodium sulfate 24.3

Sodium Toluenesulfone * 2.5

Water . 6.2

Miscellaneous (perfume, brightener, sodium anarboxymethyl cellulose) 2.0

8years in total, 0

10 parts of powdery sodium perborate tetrahydrate was mixed evenly with the spray-dried detergent granules.

A slurry containing 1.00 parts of water, 0.53 parts of Alcalase (as described) and 0.17 part of Knox gelatin (a powdery Collagen protein, which is swellable and has an average molecular weight between about 50,000 and 70,000) was made. This slurry was sprayed onto 5.28 parts of granular, anhydrous sodium tripolyphosphate

909828/154 3

whereupon the product evenly with the mixture of spray-dried detergent granules prepared as described above and powdered sodium perborate.

A control product was made which had the same composition but did not contain Knox gelatin.

Parts of the control product and the Waschmittel3 according to Example 3 were packed in Polyäthylenbeuteln and under constant conditions of 32.2 ⁰ C and 80; stored 90 days $ relative humidity, and the following results were obtained: The product according to the invention retained 75 $ of the initial protease activity ^ t, while the control product had only $ 54 of the initial activity after this time.

Example 4

Spray-dried detergent cones of the following composition were made manufactured:

component Parts by weight 34.3 Sodium alkylbenzenesulfonate
made of tetrapropylene 24.0 2.5 Sodium tripolyphosphate 18.6 6.2 Sodium silicate (SiO ₂ : Na ₂ O in the ratio
of 2: 1) 5.4 2.0 Sodium sulfate 93.0 Sodium toluene sulfonate water Miscellaneous (perfume, brightener,
Sodium carboxymethyl cellulose) all in all

A slurry containing 1.02 parts of water, 0.53 parts of Alcalaee (as described) and 0.35 parts Swift Technical Protein Colloid No. I-V (a granular collagen protein which is swellable and has an average molecular weight of about 10,000) was made. This slurry was found to be 5.10

909828/1543

Parts of granular anhydrous latrium tripolyptxosphate sprayed on, whereupon the product homogeneously with eggs as described above! here posed. Detergent was mixed "

A control product was made which had the same composition except for the fact that there were no Swift technisclies Contained protein.

The detergents were packed in simple cardboard boxes and _{stored for 30 days under constant conditions of 32 S} 2 ° G and 80% relative humidity, the following results being obtained: The product according to Example 5 retained 50% of the original proteolytic enzyme activity, while the control product ( without collagen protein) only retained 43% of its initial enzyme activity. I.

Results which correspond to those of the preceding examples are obtained if the following proteases or commercial protease products are used in equivalent amounts instead of alealase: pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, Carlsberg subtilisin, BPH '~ Subtilisin, Papa in, Piciiij Bromelin, Garboxypeptidase, Aminopeptidase, Aspergillopeptidase Λ and B, proteolytic enzymes, obtained with Streptomyces Griseus _f Maxatase, Protease B-4000, Sandoz AP 2100, CHD-Protease, Pronase-E, Pronase-P, Pronase- AP, Bioprase, Rapidase 400, Rhozyme Pi ¹ , proteolytiseh.es jänzym 7XB and Wallerstein 627-P.

Corresponding results are also obtained if the following partially hydrolyzed and solubilized gollagens are used: WSP-X-10000, Enos gelatine, Swift technical protein and collagen proteins with average molecular weights of 180,000, 150,000, 120,000, 80,000, 40,000 , 25.00O ₅ 10,000 and 5,000 «

909828/1 5A3

Results corresponding to those of Example 2 can also be obtained Achieve when using sodium bisulfate, sodium bicarbonate, or mixtures of these substances used in equivalent amounts instead of dihydrogendisodiumpyrophsophat. The same is true if the builder component, e.g. sodium tripolyphosphate, and the acidic component, e.g. dihydrogendisodium pyrophosphate, in the form of spray-dried granules can be added.

The following builder salts can be used in whole or in part of sodium tripolyphosphate in the detergents according to the invention used without reducing the enzyme stabilizing effect becomes: the sodium, potassium, ammonium, monoethanolammonium, diethanolammonium and triethanolammonium salts of the following Acids: ethylenediaminetetraacetic acid, N- (2-hydroxyethyl) -äthylendiamintijacetic acid, N- (2-hydroxyethyl) nitrilodiacetic acid, diethylenetriaminepentaessigsüue; Nitrilotriacetic acid, ethylene and ethane-1-hydroxy-1,1-diphosphonic acid, Ethane-1,1,2-triphosphonic acid, iithane-2-carboxy-1, 1-, hydroxymethane and carbonyl diphosphonic acid, Ethane-1-hydroxy- and ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3- · Propane-1,1,2,3- and propane-1,2,2,3-tetraphosphonic acid so / ie potassium tripolyphosphate. In addition, salts of polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, Methylenemalonic acid and citraconic acid and copolymers of these acids with one another or with ethylene and / or acrylic acid, e.g. in 1: 1 hol ratios and with molecular weights of 75,000, 100,000 and 125,000 (the copolymers with ethylene and / or acrylic acid have equivalent weights, based on the acid form, of 65, 70 and 75 on).

Corresponding results are also achieved if you do the following organic washing raw materials in whole or in part instead of sodium alkylbenzenesulfonate, which is made from tetrapropylene and sodium tallow alkyl sulfate sets: linear sodium dodecylbenzenesulfonate, the condensation product of 1 mole of dodecylphenol with 15 moles of ethylene oxide, dimethyldodecylamine oxide, dimethyldodecylphosphine oxide, 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypro-

909828/1543

pan-1-sulfonate and Fatrlum-S-dodecylaminopropanesulfonate.

909828/1543

Claims (12)

1) Granular detergent containing proteolytic enzymes, "consisting of (in percent by weight, based on the detergent) from: 1) about 60 Us about SQ '/ o of a mixture of an organic / ash raw material and an alkaline builder salt, the ratio of alkaline builder corn to organic / ash raw material being between about 30: 1 and about 1: 4; 2) about 0.001 to about 2.0 / 5 of a proteolytic enzyme which has its ensymatic activity in a pH range from about 5 to about 12 and at a temperature between about 10 and about 93 ⁰ C; 3) a partially hydrolyzed and solubilized collagen with an average molecular weight of at least about 5,000 in an amount sufficient to stabilize the proteolytic enzymes. 2) detergent according to claim 1, characterized in that the partially hydrolyzed and solubilized collagen have an average molecular weight of about 5,000 to about 250,000 having. 5) detergent according to claim 2, characterized in that the Mixture of about 70 to about 95 percent by weight detergent and contains less than 8 weight percent moisture, the proteolytic enzymes in an amount of about 0.01 to about 0.5 percent by weight, based on the detergent, are present and the partially hydrolyzed and solubilized Collagen has an average molecular weight of about 5,000 to about 100,000 and is used in an amount that a weight ratio of collagen to proteolytic enzyme of about 100: 1 and about 1:10 results. 4) detergent according to claim 3, characterized in that the detergent contains about 0 to about 30 ^ sodium perborate. 909878/1543 5) detergent according to Atqpruoh 4, characterized in that the partial hydrolyzed and solubilized collagen about average Has a molecular weight of about 5,000 to about 25,000 and is present in an amount such that a weight ratio from collagen to proteolytic enzyme from about 20: 1 to about 1: 1. 6) detergent according to claim 4 »characterized in that the Collagen is gelatin. 7) detergent according to claim 4 _t, characterized in that the proteolytisohe enzyme is subtilisin. 8) Granular detergent containing proteolytic enzymes, consisting of (in percent by weight, based on the detergent) a) about $ 80 to $ 98 of a mixture of an organic raw material and an alkaline builder salt in the ratio of alkaline Gertiststoffsalz to organic Wasohrotoff from about 30: 1 to Yt4, and b) about 2 to about 20 $ enzyme-containing granules, which in saturated aqueous solution have a pH value between 5 and 8 and which (in percent by weight) consist of: f 1) about 30 to about 75 $ of the alkaline builder salts, 2) about 5 to about 50 $ of an acidic component such as dihydrogendisodium pyrophosphate, Sodium bisulfate, sodium bicarbonate or mixtures of these substances, 3) 0 to about $ 20 of a synthetic organic laundry raw material, 4) about 0.01 to about 50% of a proteolytic enzyme, the enzymatic activity of which is contained in a pH range from about 5 to about 12 and at temperatures between about 10 and about 93 ⁰ O, and 5) about 0.5 to about 20 $ of a partially hydrolyzed and partially solubilized collagen, which serves to stabilize the proteolytic enzymes and a duroh- 909828/1543 has an average molecular weight of at least 5,000. 9) detergent according to claim 8, characterized in that the daduroh Mixture of organic waso raw material and alkaline builder material a mixture of a sodium alkylbenzenesulfonate, Sodium alkyl sulfate or a mixture of these two substances, in which the alkyl group is straight-chain or branched and contains about 10 to 18 carbon atoms, on the one hand and sodium tripolyphosphate. Sodium pyrophosphate or a mixture of these substances / is, the weight ratio being inorganic alkaline Geifetstoffsalz to organic Wasohrohstoff is about 15x1 to about 1s1. 10) detergent according to claim 9t daduroh characterized in that the the alkaline builder salt of the enzyme-containing granules is sodium tripolyphosphate and that the acidic component consists of dihydrogendisodiumpyrophoephat. 11) Wasohmittel naoh claim 10, daduroh characterized that the proteolytisohe enzyme is an alkaline protease and that the a substance related to stabilizing the proteolytic enzyme a partially hydrolyzed and partially soluble sewn tea Collagen with a durohsohnliohen molecular weight of about 5,000 to about 100,000 let. 12) Detergent according to claim 1 \ characterized in that the enzyme-containing granules are about 2 to about 12% of the detergent and that the alkaline protease is subtile. Door She Prooter & Gaable Ooaqpany Cincinnati, Ohio, Y.St.A. 909828/1543