LU87075A1 - AQUEOUS COMPOSITIONS CONTAINING A STABILIZED ENZYME SYSTEM FOR DISHWASHING, AND METHODS OF USE THEREOF - Google Patents

Description

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LUXEMBOURG

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Patent Application I. Application

The company called: COLGATE-PALMOLIVE COMPANY, 300 Park Avenue- * NEW YORK, New York 10022 (United States of America), represented by Monsieur Jacques.de Muyser ....... acting as agent ... ..... ? file! nti this December 15th ....... 1900 eighty-seven at 15 hours, at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent of invention relating to: "Aqueous compositions containing a stabilized enzyme system 15 for washing dishes, and their ..... methods of use. ...........-...............................

2. the description in French ............. of the invention in three copies: 3.. · Drawing boards, in three copies: 4. the receipt of the fees paid to the Office of Registration in Luxembourg, on ....... 15 awards 15c; 5. the delegation of power, dated. ... Nev; York ............ November 24: SE7 6. the successor document (authorization); declares! ntl assuming responsibility for this declaration, that the inventor (s) is (are): '' · - André CRUT2EK, Avenue du Petit Bourgogne 83, ........... .. E-SCLESSIN (Belgium) ..................

- Myriam DELVAUX, rue duGrand Marais 2, .............. E-HANNUT (Belgium) ..................... ........... ......

- Léopold LAITEM., Rue de Merdorp 2, B-ORP-JAUCHE

.............................(Belgium).................. ..... ........... ...... ...

claims (nt) for the above patent application the priority of one (or more) application (s) of t patent ............... filed (his (8iUnited States of America).

on (9). 1.5 ..... December 1986 under N ° (10). 94 .1.4 .6.4 ............

on behalf of ai) inventors elect (elect) domicile for him (her) and. if appointed, for its representative, in Luxembourg ..........

35 boulevard Royal n: requests (nt) the grant of a patent for the invention for the object described and represented in the abovementioned appendices ^ - with postponement of this grant to ............. ...6 months. <13

Lo-deposaitumandataire: "f ............ <î- / | k- Π. Depot Minutes

The aforesaid patent application has been filed with the Ministry of Economy and Middle Classes of Intellectual Property Luxembourg, on: <] December 5, 1987

Pr. The Minister of Economy and the Middle Classes ^ *. at ....... 1 ** hours / \ p. d.

\ j The head of the intellectual property department! - ..

. ...... ....

J Λ EXPUCATO iss REiÄTTVES A ’. 'FORM Oc, B £ PC <l I I I) *:; *. in ·. Ci cerLîi-.t; i additionau hr? vc! pnp; re has applied for the priiKipa patent! V ...... da:> nv · -: te. · R. rrc * 1 'ü. r adrets ·. " or Ccmaiiûcü ’. deiu .'- est estin parecuite: ou te ^ dfromtriaiior wciaie itWitML'ndiJLî ,. address of ionic sugar flusites upon request. ptrs ·. -iru-m: *: .- ^ it- nem nrenorr .. oez-ss-r m-ndata'rt aires, council tn pr ^ rneu. mduMritbs. mun: of ur power spcciin s'i '\ k, iCw. “Represents vl:. .. rri. *;., ::: -ju. · '' · Μ ->:.

'“I. 87 / B 52 71 7

‘CLAIMING PRIORITY

; ! . · The patent application / utility model

dd STATES UNITED STATES OF AMERICA

I DECEMBER 15, 1986

No. 941.464, 'i .1 i j Brief Description i filed in support of a request for • ’t

1 PATENT OF INVENTION

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Luxembourg on behalf of: colgate-palmolive company NEW YORK, New.York 10022 (United States of America);

FOR 'It N

Aqueous compositions containing a stabilized enzyme system for washing dishes / and methods of using them. "'Λ -,

AQUEOUS COMPOSITIONS CONTAINING A

STABILIZED ENZYME SYSTEM FOR 05 DISHWASHING, AND THEIR

OPERATING PROCEDURES

French patent application 87.14943 filed October 28, 1987 by the Applicant describes a reinforced aqueous liquid detergent composition for washing clothes containing an enzyme stabilizing system comprising a boron compound, an alpha-hydroxy-carboxylic acid, casein and an enzyme.

French patent application 87.12321 filed. 15 September 4, 1987 by the Applicant describes an aqueous thixotropic clay composition for washing dishes, containing aluminum stearate as a physical stabilizing agent.

The present invention relates to reinforced aqueous compositions containing a stabilized enzyme system for dishwashing. The stabilized enzyme system contains a boron compound, an alpha-hydroxy carboxylic acid, casein and an enzyme. The present invention relates, in particular, to thixotropic, aqueous liquid clay compositions for dishwashing, containing a stabilized enzyme system which comprises a boron compound, e.g. sodium borax, an alpha acid -hydroxy-carboxylic, for example lactic, tartaric or citric acid, casein and an enzyme, for example proteolytic and amylolytic enzymes. The present invention particularly relates to detergent compositions containing a stabilized enzyme system for automatic dishwashing, the enzyme of which is stable, which are physically stable and which are easy to disperse in a washing medium for cleaning dishes, glassware, '1.

4 2 porcelain / etc.

Powder detergent compositions and reinforced aqueous detergent compositions, including thixotropic compositions for dishwashing which are currently available do not contain stabilized enzyme systems.

The present invention relates to reinforced aqueous liquid detergent compositions containing an enzyme for washing dishes, which are suitable for cleaning dishes, glassware, porcelain, utensils, etc. More particularly, the invention relates to aqueous liquid detergent compositions containing an enzyme for washing dishes, which contain one or more detergency builders and which are characterized by their stability.

The automatic dishwashing compositions, also hereinafter referred to as DLAV, generally contain: 20 (1) sodium tripolyphosphate (NaTPP) to soften hard water or retain the minerals it contains and to emulsify and / or "peptize" the dirt; (2) sodium silicate to provide the alkali-nity necessary for effective detergent action and to provide protection for the glazes and patterns of the fine porcelain; (3) sodium carbonate, generally considered optional, to increase alkalinity; 30 (4) a chlorine-releasing agent to facilitate the removal of small stains: of dirt which leads to the formation of water spots and to facilitate the removal of staining soils such as tea and coffee? and 35 (5) an anti-foam / surfactant combination for 3 1, J i Λ * provide the necessary detergent activity and reduce the foam, thereby increasing the efficiency of the machine. See, for example, SDA. Detergents in Depth, "Formulations Aspects of Machine Dishwashing", Thomas Oberle 05 (1974). The cleaning products which approach the compositions described above are for the most part liquids or powders.

The use of a chlorine releasing agent in certain dishwashing compositions has however been subject to criticism, as this agent tends to react with other chemically active ingredients, in particular the surfactant (see patent US 4,115,308), thereby degrading the thixotropic or suspending agent and reducing its effectiveness. A feature of the present invention is that a chlorine releasing agent is not required in the composition for washing dishes.

The formulation of liquid compositions for dishwashing containing a stabilized enzyme has been a difficult problem. The interest which is found in incorporating enzymes in detergent compositions for washing dishes derives mainly from the efficiency which the proteolytic and amylolytic enzymes have in * decomposing the protein and starchy substances encountered on dirty dishes and utensils, so that it is easier to dispose of the consumed residual food substances such as meat sauce, eggs, tomato sauce, chocolate and others, while washing the dishes in the machine automatic. However, the enzyme substances which are suitable for dishwashing compositions, especially the proteolytic enzymes, are relatively expensive. In addition, it is known that enzymes are unstable in reinforced aqueous detergent compositions for washing clothes.

In the case of liquid laundry detergent compositions reinforced with a detergency builder of the phosphate type, it is known that the problem of the instability of the enzyme is particularly acute. The main cause is that phosphate-type detergency builders have a de-stabilizing effect on enzymes. In addition, the incorporation of a phosphate-type detergency builder into a liquid detergent composition for dishwashing poses an additional problem, namely; possibility of forming a stable composition at only one phase; the solubility of sodium tripolyphosphate, for example, being relatively limited in aqueous compositions, and very particularly in the presence of anionic detergents.

Stabilization of enzymes in strongly alkaline detergent compositions is also difficult since it is known that high alkalinity deactivates enzymes. Although it is possible to lower the pH to improve the stability of the enzymes, this to some extent negates the favorable effect of the detergency builders. The stabilized enzyme system of the present invention ensures the stability of the enzyme even at relatively high pH, up to pH 10-12. Higher pHs, for example pH 10-12, are known to give better detergency and are preferred. A reduction in the pH of the detergent composition, for example to pH 7.5-9.5, can increase the stability of the enzyme, but shortens the life of the bubble bath and the beneficial effects of the detergency builder, i.e. detergent action.

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US Patent No. 4,431,559 discloses a thixotropic composition for automatic dishwashing, comprising an aqueous solvent, a thickening agent, a source of chlorine, an anionic surfactant, adjuvant salts of detergency and a buffer system to stabilize the chlorine source.

The E. ü patent. A. No. 3,558,498 discloses a granular detergent composition for washing clothes, containing stabilized enzymes, sodium perborate trihydrate, anhydrous trisodium phosphate, anhydrous calcium sulphate and soluble or dispersible proteins having a molecular weight of 5,000 to 1,000,000, for example casein having a molecular weight of 50,000 to 200,000.

US Pat. No. 3,560,392 discloses a granular laundry detergent composition containing an organic detergent, an alkaline detergency builder salt, a stabilized enzyme and a stabilizing amount of protein collagen having a molecular weight from 5,000 to 250,000.

The E. ü patent. A. No. 4 238 345 made con-. A liquid detergent composition for washing clothes is produced, in which the enzyme is stabilized by the addition of an antioxidant and a hydrophilic polyol having 2 to 6 hydroxyl groups. The patentee states in column 1 that calcium salts associated with proteins and glycerol associated with proteins have been used to form enzyme stabilizing systems in aqueous liquid detergents for washing clothes.

Patent application GB-A-2 079 305 discloses a reinforced aqueous liquid detergent composition containing an enzyme for washing clothes, in which the enzyme is stabilized by a mixture of a polyol and boric acid.

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6

The present invention relates to an aqueous liquid composition reinforced with a polyphosphate for dishwashing / containing a stabilized enzyme system which comprises a boron compound, an alpha-hydroxy-carboxylic acid, a protein material, for example casein, and an enzyme.

Stabilization of the enzyme is achieved by premixing a mixture of boron compound and alpha-hydroxy carboxylic acid with a mixture of enzyme and casein in order to block the catalytic sites of the enzyme with casein and , simultaneously, blocking the structure of the enzyme with the mixture of the boron compound and the alpha-hydroxy-carboxylic acid.

In addition to providing very good protease stabilization, the enzyme stabilizer system. the present invention exerts a very good stabilization of amylases, which allows the use of double stabilized systems based on protease and amylase in very alkaline detergent compositions.

The effective stabilization of amylase activity is surprising, since it should be expected that all amylase activity will be destroyed at pH above 9.

According to the present invention, the washing in china of dirty dishes and utensils is carried out by bringing the dishes and utensils into contact with a very powerful reinforced aqueous liquid composition for washing dishes, containing the stabilized enzyme system.

The aqueous liquid dishwashing compositions of the present invention are capable of satisfactorily cleaning dishes and utensils containing both oily and particulate food soiling. In addition, the »7:’ · ϊ *; i i • Vs * · described compositions can be used for the pre-soaking of very dirty dishes which must be washed in an automatic dishwasher.

The present invention is based on the discovery that a stabilized enzyme system comprising a boron compound, an alpha-hydroxy-carboxylic acid, a protein substance, for example casein, and an enzyme, has a clear effect and powerful enzyme stabilizer in aqueous liquid compositions for dishwashing.

In one embodiment, the present invention relates to an aqueous liquid dishwashing composition comprising an enzyme stabilizing system and a suspension of a phosphate-type detergency builder salt in the aqueous liquid detergent based anionic surfactant.

In another embodiment, the present invention relates to a thixotropic aqueous liquid clay composition for washing the vessel, comprising an enzyme stabilizing system and a suspension of a phosphate-type detergency builder salt. in aqueous liquid detergent based on anionic surfactant.

We have discovered that an enzyme stabilizer system consisting of a boron compound, an alpha-hydroxy carboxylic acid, a proteinaceous substance, e.g. casein, and an enzyme, exerts stable effective enzyme activity for relatively long periods of time in aqueous liquid dishwashing compositions.

The dishwashing compositions of the present invention are physically stable. The aqueous liquid detergent composition of the present invention is easy to pour, easy to dose and easy to use. to be placed in an automatic dishwasher.

It would be interesting to have an aqueous liquid composition, possibly thixotropic with clay, for washing the vessel-05 le, which contains a stabilized enzyme system and possibly a physical stabilizing agent.

It is therefore an object of the present invention to provide an aqueous liquid dishwashing composition containing a stabilized enzyme system.

Another object of the invention is to provide a thixotropic aqueous liquid clay composition for washing dishes, containing a stabilized enzyme system · '··.

Yet another object of the invention is to provide a stabilized enzyme system containing a boron compound, an alpha-hydroxy carboxylic acid, casein and an enzyme, intended to be added to aqueous liquid compositions, optionally thixotropes, for washing dishes, in order to communicate to said compositions an effective enzymatic cleaning activity of the proteolytic and / or amylolytic type.

Yet another object of the invention is to improve the physical stability of aqueous thixotropic gel liquid compositions for washing dishes containing enzyme stabilized systems, by incorporating into a thixotropic clay composition for washing dishes, a small effective amount of a metal salt of fatty acid, as a stabilizing agent, for example aluminum stearate, to inhibit sedimentation of suspended particles and prevent phase separation .

These and other objects of the invention will become more apparent from the following detailed description of the invention and its preferred embodiments and are achieved by incorporating a stabilized enzyme system. in a thixotropic aqueous composition, for example normally in the gel state. In order to improve the physical stability of the dishwashing composition, there may be included a small effective amount of a physical stabilizer, for example a fatty acid or a metal salt of fatty acid. More particularly, according to a preferred embodiment of the invention,. there is provided a composition, · normally in the gel state, for washing dishes, in which are incorporated a stabilized enzyme system containing a · compound of boron, an alpha-hydroxy-carboxylic acid, casein and an enzyme, and a stabilizing amount of a long chain fatty acid metal salt which is effective in inhibiting sedimentation of suspended particles.

The present invention relates to a phosphate reinforced aqueous liquid dishwashing composition containing a relatively simple stabilized enzyme system which comprises a boron compound, an alpha-hydroxy carboxylic acid, a proteinaceous substance. example casein, and an enzyme. The enzyme stabilizer system stabilizes the active enzyme ingredient for relatively long periods of time, so that small amounts of expensive enzymes can be used.

The present invention relates to a compound. An aqueous liquid based on anionic surfactant, reinforced with a phosphate, for washing dishes, containing a stabilized enzyme which can be used at high effective pHs of the order of 10-12.

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The present invention also relates to a powerful and effective composition for washing dishes, which does not require the use of a chlorinated compo-sê.

According to a preferred embodiment of the present invention, there is provided an aqueous composition, normally in the gel state, for automatic washing of dishes, endowed with thixotropic properties, which comprises, on a weight basis: 10 (¾ ) 8 to 35 I of tripolyphosphates of alkali metals; (b) 0 to 20%, for example 2.5 to 20%, of sodium silicate; (c) 0 to 9% alkali metal carbonate; (D) 0 to 5%, for example 0.1 to 5%, of a detersive action material dispersible in water; (e) a thixotropic clay thickening agent, in a proportion sufficient to provide the composition with a thixotropic index of 0 to 10.0, for example about 2.5 to 10; (f) 0.5 to 2.0% of boron compound; (g) 1.5 to 4.0% alpha-hydroxy carboxylic acid; (h) 1 to 4.0% casein; (I) 0.5 to 2.0% enzyme? (j) 0 to 5% foam inhibitor; (k) 0 to 8% sodium hydroxide; (l) 0 to 2% of a long chain fatty acid metal salt; and 30 (m) the rest of the water.

Also related to this aspect, the invention relates to a method for cleaning dishes in an automatic dishwasher with an aqueous washing bath containing an effective amount of the liquid detergent composition for automatic washing of f * 11 dishes (DLLAV) as described above. According to this aspect of the invention, the DLLAV composition can be easily poured into the dispensing cup of the automatic dishwasher and, in just a few seconds 05, thicken quickly to return to its normal state of gel or paste so to hold firmly inside the dispensing cup until shear forces are applied to it again, as under the effect of the water jet sent by the dishwasher.

In accordance with the present invention, the activity of the enzyme is stabilized for a long period of time, so that small amounts of: the enzyme provide effective enzymatic cleaning activity. The enzymatic activity is stabilized by the addition of small effective amounts of a stabilized enzyme system comprising a boron compound, an alpha-hydroxy carboxylic acid, a proteinaceous substance, for example casein, and an enzyme. The stabilized enzyme system is used in anionic-type aqueous compositions reinforced with phosphates.

Stabilized Enzyme System The stabilized enzyme system is preferably prepared separately and then added to the dishwashing composition.

The stabilized enzyme system is preferably prepared according to a three-step procedure described below.

1. A boron compound is added to an alpha-hydroxy-carboxylic acid or salt to obtain a first mixture.

2. Add the proteinaceous substance, for example casein, to an aqueous alkaline solution and add the enzyme to the aqueous alkaline solution to make a second mixture.

3. The mixture of boron compound and alpha-hydroxy-arboxylic acid obtained in step 1 is then mixed with the mixture of protein substance and of enzyme obtained in step 2 to obtain a premix which is the stabilized enzyme system of the present invention.

The mixture from step 1 and the mixture from step 2 above can each be added separately to the dishwashing composition, but the best enzyme stabilization results are obtained by mixing the mixtures of steps 1 and 2, then adding the premix obtained to the washing composition of the vessel.

Although the Applicant does not wish to be bound by any theory as to how the stabilized enzyme system works, it is believed that the boron compound reacts with alpha-hydroxycarboxylic acid or the acid alpha-hydroxy-polycarboxylic to form a boric acid ester. The boric acid ester is believed to react with the enzyme and. block its structure in the active configuration, thereby protecting it from denaturation. The proteinaceous substance is believed to block the catalytic sites of the enzyme and thereby prevent the digestion of other enzyme molecules during storage of the product.

The stabilized enzyme system comprises: a boron compound, for example b.orax, in an amount of 0.4 to 2.5, preferably 0.75 to 2.0 and better still 0.9 to 1 , 2, parts by weight; - an alpha-hydroxy-carboxylic acid, in an amount of 1 to 5, preferably 1.5 to 4.0 and better still 1.8 to 3.6, parts by weight; - a proteinaceous substance, for example casein, in an amount of 1 to 6.0, preferably 1 to 4.0, for example about 1.0 to 2.0, parts by weight; and - an enzyme in an amount of 0.5 to 3.0, preferably 0.5 to 2.0 and more preferably 0.5 to 1.0, parts by weight.

The weight ratio of alpha-hy-droxy-carboxylic acid to boron compound can be from 7: 1 to 1: 1, preferably from 4: 1 to 1: 1 and better still from 3: 1 at 2: 1.

The weight ratio of the proteinaceous substance, for example casein, to the enzyme can be from 8: 1 to 1: 1, preferably from 4: 1 to 1: 1 and better still from 4: 1 to 2: 1.

A preferred stabilized enzyme system of the present invention comprises the following components in the amounts indicated.

Parts by Weight

Borax (Na ^ O. ^ 10H20) 0.75 to 2.0 20 Alpha-hydroxy-carboxylic acid 1.5 to 4.0

Casein 1.0-4.0

Enzyme 0.5 to 2.0

The stabilized enzyme system can be added to the dishwashing composition in an amount of 10 to 30 parts by weight of stabilized enzyme system per 90 to 70 parts by weight of detergent composition, preferably 15 to 25 parts by weight of stabilized enzyme systems for 85 to 75 parts ai weight 30 of acnepmtdai deteiganbe, and still 15 to 20 parts if perieb of stabilized enzyme system pxir 85 to 80 parts by weight of detergent composition. The stabilized enzyme system is added to the dishwashing detergent composition such that the weight percentages of the active ingredients of the stabilized enzyme system in the detergent composition are equivalent to the parts by weight mentioned above. active ingredients in the stabilized enzyme system.

05 A detailed description of the stabilized zyme system is presented in the aforementioned French patent application 87.14943. ·

The stabilized enzyme system of the present invention can be used in aqueous liquid compositions for dishwashing, in aqueous thixotropic liquid compositions for dishwashing and in granular or powdered compositions for washing dishes.

The stabilized enzyme systems of the present invention are, in a preferred embodiment, added to aqueous thixotropic liquid compositions for dishwashing. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Acids- Alpha-Hydroxy — Carboxylic 2

The alpha hydroxy hydroxy carboxylic acids which can be used in the present invention are the organic carboxylic acids having 3 to 8 5 carbon atoms, including 1 to 3 carboxylic acid groups, and 1 to 3 hydroxyl groups. .

7

Preferred carboxylic acids are 8 alpha-hydroxy carboxylic acids having 3 to 6 carbon atoms, including 1 to 3 carboxylic acid groups, and 1 to 2 hydroxyl groups. Suitable alpha-hydroxy carboxylic acids include 12 malic acid (ISOCCHOHCHÿCOOH), 13 tartaric acid (HOOCCHOHCHOHCOOH), 14 lactic acid (HOOCCHOHCHLj) and 15 citric acid (HOOCCE ^ C (OH) COOHCE ^ COOH).

16

Preferred alpha-hydroxy carboxylic acids are I t4 ύ.

15. tartaric, lactic and citric acids. Citric acid is most appreciated. The alpha-hydroxy carboxylic acids can be used as such or in the form of their alkali metal salts, such as the sodium or potassium salts.

Boron compounds

The boron compounds which are used in the dishwashing compositions of the present invention are those which are soluble in water and which, when added to water, form boric acid or a metal salt alkaline boric acid. Boron compounds that can be used; . include boric acid, boric oxide or an ÿ 15 alkali metal borate. Suitable alkali metal borates are sodium and potassium ortho-, pyro- and metaborates, polyborates and borax (^ 23 ^ 0 ^. 10H20). Preferred boron compounds are boric acid, sodium borate (Na ^ BO ^) and borax (Na2B40 ^. ÎOI ^ O).

Enzymes

The enzymes to be incorporated into the dishwashing compositions of the present invention may be proteolytic or amylolytic enzymes or mixtures thereof. Proteolytic enzymes suitable in the present invention include various commercial preparations in liquid, powder or paste form, which have been adapted for use in detergent compositions.

Although incorporating the enzyme into the composition is more convenient in liquid form, enzymes in paste form have been found to be useful. Appropriate enzyme preparations in form,. * i '*' '"4! 4 i * 16 me liquid include "Alcalase" and "Esperase" sold by Novo Industries, Copenhagen, Denmark? "Maxatase". and "Maxacal" sold by Gist-Brocades, Delft, Netherlands; and "Optimase" sold by Miles Kali Chemie. Suitable proteolytic enzymes include sub-tilisin, bromelain, papain, trypsin and pepsin. Suitable enzymes include a liquid protease and a liquid amylase. The enzymes are preferably used in the form of their solutions. A preferred enzyme is Esperase 8L in the form of a solution. Appropriate preparations of alpha-amyla-. in liquid form are those sold by Novo Industries and Gist-Brocades under the manufacturers' brands, respectively "Termamyl" and "Maxamyl". A preferred enzyme is Termamyl 120L. "Esperase" 8L is preferred for the present compositions because of its activity at high pH values which correspond to the reinforced detergent compositions. Another preferred enzyme is Esperase8.0L due to its high activity at 60 ° C and its low activity at room temperature. In addition, Esperase 8.0L is stable at high pH, which allows a higher pH in the final product and a better detergent action. 1 2 3 4 5 6 7 8 9 10 11

Protein Substance 2 One of the components of the enzyme stabilizer system 3 of the present invention is a protein substance 4, for example casein. The protein substances are used in the form of their water-soluble alkali metal salts (for example sodium or potassium 7) and / or are dispersed in an aqueous medium to which the enzyme is added.

9

Proteins which are soluble or dispersible in water are used herein in an amount effective to stabilize the enzymes. Examples of ’‘ \ '* 4 17 proteins which are soluble or dispersible in water and which can be used here include casein (average molecular weight 50,000 to 200,000); Wilson's Protein WSP-X-1000 (a solubilized collagen 05 with an average molecular weight of about 10,000) and Wilson's Hydrolysate Cosmetic 50, both marketed by Wilson's Pharmaceutical & Chemical Company; and Collagen Hydrolyzate Cosmetic 50, marketed by Maybrook, Inc. A preferred casein-like protein 10 is sold under the trademark "Sodium Caseinate" by Bridai (France) or Denâ, A.G. (R. F. A.).

Sodium Caseinate is a mixture of several caseins of different molecular weights. Proteins, for example casein, are normally available as powders. Proteins such as casein have the structure of long chemical chains. In the powder state, the chains are folded back on themselves and form hydrogen bonds which maintain the protein in a globular form. Unraveling or denaturing the protein involves breaking these bonds to form a looser, less ordered structure. Proteins can be denatured by cooking in boiling water and by the use of acids, alkalis and various detergents. Detangled or denatured proteins are more easily digested by enzymes and therefore produce a better stabilizing effect, that is to say, provide better stability to the enzyme.

Denaturation makes the protein more effective as a stabilizer. The protein, for example casein, is used in an amount sufficient to stabilize the enzyme activity.

Detergent Composition - for Dishwashing 35 In general, the effectiveness of corn. 18 'Λ4 * + aqueous thixotropic clay positions for washing dishes is related: (a) to 1' alkalinity, (b) to solubility in the washing medium, and 05 (c) to inhibition of foam. It is preferred here that the pH of the DLLAV composition is at least about 9.5, more preferably about 10.5 to 12.5, and at best at least about 11.5. At relatively lower pH values, the dishwashing detergent is too viscous, i.e. almost solid, and therefore does not readily fluidize under shear forces at the intensities at which they are generated in the distributor cup under normal machine operating conditions. In a few words, the composition loses most, if not all, of its thixotropic character. The addition of NaOH is therefore often necessary to raise the pH to the above ranges, and to improve the flowability properties. The presence of carbonate is also often necessary here, as it acts as a buffer that helps maintain the desired level of pH. An excess of carbonate should however be avoided, as this could result in the formation of needle-like carbonate crystals, which would compromise the stability, thixotropy and / or detergency of the DLLAV product, as well as its ability to be distributed from, for example, from vials into compressible tubes. Another function of caustic soda (NaOH) is to neutralize the foam inhibitor of the phosphoric acid ester type or phosphonic acid, if present. Typical proportions of NaOH and sodium carbonate in the DLLAV composition are respectively about 0.5 to 3 percent by weight and about 2 to 9 percent by weight, although it should be noted that Sufficient alkalinity can be provided by NaTPP and sodium silicate. Sodium silicate can be used in proportions of 0 to 20 percent by weight, preferably 2.5 to 20 percent by weight and better still 5 to 15 percent by weight.

NaTPP is used in the DLLAV composition in proportions of about 8 to 35 percent by weight, preferably about 20 to 30 percent by weight. The NaTPP can be anhydrous or hydrated, which includes the stable hexahydrate where the hydration level of 6 corresponds to about 18% by weight of water or more. In fact, having regard to the stability of the hexahydrate, the presence of a little hydrata- water. tion is very effective in that it is believed to serve to form germs of stable hexahydrate which ac-. celebrate the hydration and solubilization of the remaining NaTPP particles. If only hexahydrate is used, the detergent may be too liquid and have little, if any, thixotropic character. Conversely, if only anhydrous NaTPP is used, the product may, in certain cases, be too thick and therefore inappropriate. Particularly preferred DLLAV compositions are obtained, for example, when a weight ratio of NaTPP (anhydrous to hexahydrate) of 0.5: 1 to 2: 1 is used, with values around 1: 1 being most preferred.

Inhibition of foam is important for increasing the efficiency of the dishwasher and minimizing the destabilizing effects which may occur due to the presence of excess foam in the water during use. . The foam can be sufficiently reduced by a judicious choice of the type and / or the quantity of detersive material, this component being the main producer.

4 A

I.

i of foam. The degree of foaming also depends somewhat on the hardness of the washing water contained in the machine, so that an adequate adjustment of the proportions of NaTPP, which exerts a water softening effect, can help to obtain the desired degree of foam inhibition. At best, however, a depressant or foam inhibitor can be included in cases where a low-foaming DLLAV product is desired. Particularly effective foam inhibitors are the alkyl esters of phosphonic acids of the formula: 0

HO - P - R

15 -

GOLD

supplied, for example, by BASF-Wyandotte (PCUK-PAE), and in particular the acidic alkyl esters of phosphoric acid corresponding to the formula: 0 il HO— P - OR 25

GOLD

supplied, for example, by Hooker (SAP) and Knapsack (LPKn-158), where one or both of the R groups in each type of ester can independently represent C1-C20 alkyl groups. mixtures of esters of the two types or mixtures of mono- and diesters of the same type. A particularly preferred foam inhibitor is a mixture of 35 acid phosphates of mono- and di (C1-C6 alkyl) 21 i -4 ^ such as a 1.2 / 1 mixture of mono-stearyl acid phosphates distêaryl (Knapsack). If used, typical proportions of foam inhibitor in the composition are 0.1 to 5 percent by weight, preferably about 0.1 to 0.5 percent by weight, the ratio by weight of the detersive component (d) to the foam inhibitor (j) generally being in the range of about 10: 1 to 1: 1 and preferably about 4: 1 to 1: 1. Other defoamers which can be used include, for example, known silicones.

Sodium silicate, which gives alkalinity and provides protection for hard surfaces, such as enamels and patterns from fine porcelain, is used in the composition in an amount ranging from about 2.5 to 20 percent by weight, preferably about 5 to 15 percent by weight. The sodium silicate is generally added in the form of an aqueous solution, the Na 2 O: SiO 2 ratio of which is preferably about 1: 2.2 to 1: 2.8.

At this point, it should be noted that most of the other components of the present composition, notably NaOH, the foam inhibitor and the thixotropy thickener, are also often added in the form of an aqueous dispersion or solution. previously prepared.

The detersive materials useful herein are water dispersible surfactants of the anionic organic compound, amine oxide, phosphine oxide, sulfoxide or betaine types. Anionic surfactants are preferred. The surfactants, for example anionic surfactants, are used in proportions ranging from about 0.1 to 5%, preferably from about 0.3 to 2.0%. Particularly preferred surfactants here are the mono- and / or di (C 1 -C 22 alkyl 1! 22) - (diphéhyl oxide) -mono- and / or linear or branched alkali metal disulfates available in the art. trade, for example under the names DOWFAX (Trade Mark) 3B-2 and DOWFAX 2A-05 1. In general, paraffinsulfonates tend to reduce, if not suppress, thixotropy and have been found to excessively increase viscosity by causing ' serious problems with shear forces. In addition, the surfactant must be compatible with the other ingredients of the composition. Other suitable surfactants include alkylsulfa-tes, alkylsulfonates and alkylarylsulfonates with primary alkyl group, and alkylsulfates with alkyl group! secondary. Examples are sodium (C1Q-C 15 -alkyl) alkyl sulphates such as sodium dodecyl sulphate and sodium (tallow alkyl) sulphate; (C 1 -C 4 alkane) sodium sulfonates such as sodium hexadecyl-1 sulfonate; and the (C 1 -C 4 alkyl) benzenesulfonates SO (4 µm such as sodium do-decylbenzenesulfonates. The corresponding potassium salts can also be used. Examples of suitable alkyl sulfonates are the (C 1 primary alkyl ^ -C ^) sodium and potassium sulfonates, sodium (C10-C ^ normal primary alkyl) sodium sulfonate being preferred.

As other suitable surfactants or detergents, amine oxide type surfactants typically have the structure R2R1N = 0, in which each R represents a lower alkyl group, for example methyl, and R1 represents a long chain alkyl group having 8 with 22 carbon atoms, for example a lauryl, myristyle, palmityl or cetyl group. Instead of an amine oxide, a surfactant of the corresponding phosphine oxide I ^ R ^ O 35 or type can be used. sulfoxide RR1S0. Betaine type surfactants 23 r., * "! ·). 'typically have the structure ï ^ R ^ N-R'COO ", in which R' represents a lower alkylene group having 1 to 5 carbon atoms. Specific examples of these surfactants are lauryl-dimethylamine, 05 myristyl dimethylamine oxide, the corresponding phosphine oxides and sulfoxides, and the corresponding betaines, including dodecyl dimethyl ammonium acetate, tetradecyl diethyl ammonium pentanoate, hexadecyl dimethyl ammonium hexanoate, etc. To ensure biodegradability, the alkyl groups of these surfactants should be linear, and such compounds are preferred.

Surfactants of the above types, all well known in the art, are for example described in; 15 the patents of E. ü. A. NQ 3,985,668 and 4,271,030.

Thixotropic thickening agents, i.e. thickening or suspending agents which impart thixotropic properties to an aqueous medium, are known in the art and can be organic or inorganic, water soluble, dispersible in water. water or colloidogenes, and monomers or polymers, and they must obviously be stable in these compositions, in particular with respect to the high alkalinity. Thixotropic thickeners which are particularly preferred 25 generally comprise colloidal mineral clays of the smecti-te and / or attapulgite types. Organic clays can also be used as thixotropic thickeners.

These materials have been used generally in proportions of about 1.5 to 10, preferably 2 to 5, percent by weight to impart the desired thixotropic properties and Bin-gham plasticity to DLLAV compositions described in the Applicant's previous applications GB-2 116 199A 35 and -2 140 450A.

I „24

In accordance with the present invention, proportions of the colloidogenic mineral clays of the smectite and / or attapulgite types included in the range of approximately 0.25 to 5%, preferably 0.50 to 05 4.0, in particular 1.0 to 3 %, are generally sufficient to obtain the desired thixotropic properties and the Bingham plasticity character. Smaller amounts of the thixotropy agent can be used when used in conjunction with a metal salt of fatty acid serving as a physical stabilizer.

Smectite clays include the various varieties of montmorillonite (bentonite), hectorite, attapulgite, smectite, saponite and others. Montmorillonites are preferred and are available under commercial brands such as Thixogel (Trademark Deposited) No. 1 and Gelwhite (Trademark Deposited) GP, H, etc., from Georgia Kaolin Company; and ECCAGUM (Trademark Registered) GP, 8 PM, etc., at Luthern Clay Products. Attapulgites include materials available under the Attagel trade mark, that is, Attagel 40, Attagel 50 and Attagel 150, from Engelhard Minerais and Chemicals Corporation.

Mixtures of the smectite and attapulgite types in weight ratios of 4: 1 to 1: 5 are also useful here. Thickening or suspending agents of the above types are well known in the art and are for example described in U.S. Patent No. 3,930,985,668 referred to above. Abrasives or polishing agents should be avoided in DLLAV / compositions as they can damage the surface of fine dishes, crystal, etc.

The proportion of water contained in these compositions must obviously be neither excessive to the point of producing too low a viscosity and too great a fluidity, nor insufficient to the point of generating too high a viscosity and a too weak flowability, the thixotropic properties being in one case or the other diminished or destroyed. This proportion is readily determined by routine experimentation in any particular case, and is generally in the range of about 35 to 65 percent by weight, preferably about 10 40 to 55 percent by weight. weight. It is also preferable that the water is deionized or softened.

Unless otherwise indicated, the description of the DLLAV product generally conforms to that of the compositions described in the patent applications GB-2 116 199A and 2 140 450A of the Applicant. “The DLLAV products of the previous GB- applications 2,166,199A and -2,140,450A have improved rheological properties, as evaluated by determining the viscosity of the product as a function of the shear rate. These compositions have a higher viscosity at low shear rate and a lower viscosity at high shear rate; the results indicating that effective fluidization and gelation occurs largely within the limits of the range of shear rates encountered in current automatic dishwashers. In practical terms, this results in better pouring and processing characteristics, as well as less leakage in the dispenser cup of the machine, compared to the liquid or gel DLAV products of the prior art. For shear rates corresponding to 3 to 30 rpm, the viscosities (Brookfield) ranged respectively from approximately 10,000-30,000 mPa.s to approximately 3,000-7,000 35 mPa.s, as measured at the room temperature using '* *! 26 of a Brookfield LVT viscometer after 3 minutes using a No. 4 spindle. A shear rate of 7.4 s-1 corresponds to a spindle speed of approximately 3 rpm. An increase of approximately 10 times the shear rate results in an approximately 3 to 9-fold reduction in viscosity. With the prior art DLAV gays, the corresponding reduction in viscosity was only about 2 times. In addition, with these compositions, the initial viscosity noted at about 10 rpm was only about 2,500 to 2,700 mPa.s. These compositions of the aforementioned prior applications thus manifest fluidization thresholds at lower shear rates and of a markedly greater magnitude in terms of incremental increase in the shear rate as a function of the incremental decrease in viscosity. This property of the DLLAV products of the above-mentioned earlier applications is summarized by a thixotropy index (IT) which is the ratio of the apparent viscosities at 20 3 rpm and at 30 rpm. The compositions of these prior mandes have an IT of 2 to 10. The DLLAV compositions tested showed a massive and rapid return to the consistency of the state of rest upon the cessation of the shear force.

The French patent application 87.12321 mentioned above is based on the discovery that the physical stability, that is to say the resistance to phase separation, to sedimentation, etc., of aqueous liquid DLAV compositions Patent claims GB-2,116,199A and -2,140,450A can be significantly improved without adversely affecting and, in some cases, improving their rheological properties by adding to these compositions a small but effective amount of a metal salt of a long chain fatty acid.

* »27

As an example of improving the rheological properties, it has been found that at low shear rates, for example at a spindle speed of about 3 rpm, the apparent viscosities can.

05 often be increased 2 to 3 times by incorporating a proportion as small as 0.2% or less, for example 0.16%, of the metal salt of stabilizing fatty acid. At the same time, physical stability can be improved to such an extent as within a long period of time, twelve weeks or more, in temperature intervals ranging from near freezing to 40 °. C or more, the compositions containing the metal salts of acids. Fat stabilizers undergo no ob-servable phase separation.

The preferred long chain fatty acid metal salts are those presented in the above-mentioned application 87.12321. Suitable metal salts of fatty acids are the metal salts of higher aliphatic fatty acids having about 8 to about 22 carbon atoms, preferably about 10 to 20 carbon atoms, and most preferably about 12 to 18 carbon atoms, including the carbon atom of the fatty acid carboxyl group. The aliphatic radical can be saturated or unsaturated and it can be straight or branched. Straight chain saturated fatty acids are preferred. Mixtures of fatty acids can be used, such as those from natural sources, such as tallow fatty acid, coconut fatty acid, soy fatty acid, etc., or from synthetic sources which provide provision of industrial manufacturing processes.

Thus, examples of the fatty acids from which the stabilizing metal salts can be prepared include, for example, decanoic acid, dodecanoic acid, palmitic acid, myristic acid, acid stearic, oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid, soy fatty acid, mixtures of these acids, etc. Stearic acid and mixtures of fatty acids are preferred.

Preferred metals are polyvalent metals such as magnesium, calcium, aluminum and zinc.

Many of these metal salts are commercially available. By. for example, aluminum salts are available under the. form with three acid residues, for example aluminum stearate in the form of aluminum tristearate Al (C ^ H ^ COO) ^ · Salts 15 with a single acid residue, for example aluminum monostearate Al (OH) ^ (C ^ H ^ COO), and the salts with two acid residues, for example aluminum distearate Al (OH) (C ^ H ^ COO) 2, and mixtures of two or three salts with one, two and three acid residues can be used for metals which, such as Al, have the valence +3, and mixtures of salts with one and two acid residues can be used for metals which , such Zn, have the valence +2.

The polyvalent salts of fatty acids preferred as stabilizers are calcium stearate, i.e. calcium distearate, magnesium stearate, i.e. magnesium distearate, stearate d aluminum, i.e. aluminum tristearate, and zinc stearate, i.e. zinc di-stearate.

Naturally, the use of fatty acids as stabilizing agents offers, because of their well known low toxicity, a particular advantage for the DLLAV compositions, as well as for all the other applications in which the composition of the invention. 29 tion is or is likely to come into contact with objects used to handle, store or serve food products or is in any other way likely to come into contact with human beings 05 or animals or to be consumed by them. In this respect, calcium stearate, i.e. calcium distearate, and magnesium stearate, i.e. magnesium distearate, are particularly preferred since they are generally harmless food additives.

The proportion of metal salts of stabilizing fatty acids suitable for obtaining the desired improvement in physical stability depends on factors such as the nature of the fatty acid salt, the nature. 15 re and the proportion of thixotropy agent, detergent agent, mineral salts, in particular TPP, and other ingredients of the DLLAV product, as well as the conditions provided for storage and transport.

In general, however, proportions of stabilizers of the metal salt type of fatty acid ranging from approximately 0.2 to 2%, preferably from approximately 0.5 to 1.0%, and with very particular preference. about 0.5 to 0.8 I, provide long-term stability and the absence of phase separation at rest or during transport at low and high temperatures, as required for a product acceptable to the consumer. from a commercial point of view.

Depending on the proportions and types of physical stabilizers and thixotropic agents, the addition of the metal salt of fatty acid not only increases physical stability, but also provides a simultaneous increase in apparent viscosity. Fatty acid to thixotropic agent ratios ranging from about 0.08 to 0.4 percent by weight * * V * 30 fatty acid to about 1.3 to 2.5 percent by weight Weights of thixotropy agent are generally sufficient to provide these simultaneous benefits and, therefore, the greatest preference is given to the use of these ingredients in these reports.

According to one of the methods of manufacturing these compositions, it is necessary to dissolve or disperse. First of all all the mineral salts, i.e. carbonate (if used), silicate and tripolyphosphate , in the aqueous medium. The thickening agent (if used) is added just before the stabilized enzyme system. The foam inhibitor (if used) is previously prepared in the form of an aqueous dispersion, as is the thickening agent. The foam inhibitor dispersion, caustic soda (if used) and mineral salts are first mixed at high temperature to form an aqueous solution (deionized water), then cooled, with stirring at the start at the end of the operation. The surfactant, the stabilizing fatty acid salt and the thickening agent dispersion are then added at room temperature to the cooled solution (20-25 ° C). The stabilized enzyme system of the present invention is added last.

The total salt concentration (NaTPP, sodium silicate and carbonate) is generally about 20 to 50 percent by weight, preferably about 30 to 40 percent by weight, in the composition. The stabilized enzyme system generally constitutes about 15 to 25 parts by weight, preferably 15 to 20 parts by weight, of the composition.

Another method for mixing the ingredients of the DLLAV compositions consists first of all in forming a mixture of water, the soft-foam inhibitor (if used), detergent, * 31 * *

Physical stabilization (if used), for example a fatty acid salt, and thixotropy agent (if used), for example a clay. These ingredients are mixed together under high shear conditions, preferably starting at room temperature, so as to obtain a uniform dispersion. The remaining ingredients are incorporated into this premix under low shear mixing conditions. For example, the required amount of premix is introduced into a low shear mixer, then the remaining ingredients are added, while mixing, either successively or simultaneously. Preferably, the ingredients are added successively, although it is not essential to complete the addition of a given ingredient in its entirety before starting to add the next ingredient. In addition, one or more of the ingredients can be divided into several portions and added at different times. Good results have been obtained by adding the remaining ingredients in the following order: sodium hydroxide, alkali metal carbonate, sodium silicate, alkali metal tripolyphosphate (hydrated), alkali metal tripolyphosphate (anhydrous or containing at most 5 % water), hy-25 sodium hydroxide and finally stabilized enzyme system.

Other conventional ingredients may be included in these compositions in small proportions, generally less than about 3 percent by weight, for example a perfume, hydrotropic agents such as benzene-, toluene-, xylene-, and cumene -sodium sulfonates, preservatives, coloring matters and pigments, etc ,, all being obviously stable with respect to the high alkalinity (property common to all the components). Particularly preferred dyestuffs * · * '* 4 · 32 are chlorinated phthalo-cyanines and aluminosilica polysulphides which communicate respectively pleasant green and blue hues. Ti * ^ can be used to blan-05 chir or neutralize degraded shades.

The liquid DLAV compositions of the present invention are readily used in a known manner for washing dishes, kitchen utensils, etc., in an automatic dishwasher fitted with a suitable detergent dispenser, in an aqueous washing bath. containing an effective amount of the composition.

Although the invention has been described in particular in the aspect of its application to aqueous thixotropic detergents with clay for automatic dishwashing, those skilled in the art will readily appreciate that the advantages obtained by the addition of the stabilized enzyme system apply equally to aqueous liquid compositions and to powdered compositions for dishwashing.

The invention can be practiced in various ways and a number of particular embodiments will be described for illustrative purposes in the examples below where all amounts and proportions are expressed by weight relative to the weight of composition, unless otherwise indicated.

EXAMPLE '1' A stabilized enzyme system was prepared in accordance with the present invention by the following procedure.

(1) 12.6 grams of sodium borate (Na3B03) are added to 56.1 grams of tartaric acid in 90 grams of water, while stirring. We neutralize the me- 33 * * ·. Change to about pH 7 with 56/1 grams of NaOH (50 I solution).

(2) 60 grams of casein / supplied by Bridel are added to 270 grams of water containing 1/8 grams of 05 NaOH / while stirring and heating. After complete dissolution, 15 grams of Esperase 8.0L are added at 50 ° C. and 9 grams of Termamyl 120L are added at room temperature, to obtain a casein-enzyme mixture.

(3) The mixtures obtained in steps (1) and (2) above are mixed together to obtain the premixed stabilized enzyme system of the present invention.

The entire premixed stabilized enzyme system, i.e., about 570.6 grams, can be incorporated into an aqueous liquid dishwashing composition or into a thixotropic aqueous liquid clay composition. ; or when washing - dishes so as to obtain about 3000 g of composition for washing dishes, amount in which the constituents of the stabilized enzyme system of the present invention are present in the following proportions.

Percent by Weight

Na3B03 .0.4

Tartaric acid 1/9

Casein 2.0 30 Esperas.e 8.0L 0.5

Termamyl 120L 0.3

The dishwashing compositions which contain the stabilized enzyme system of the present invention have been found to be effective in cleaning 34 "*> *" of dirty dishes, even in the absence of active chlorine-providing compounds.

EXAMPLE 2 A stabilized enzyme system containing the following ingredients is prepared according to the procedure of Example 1. -

Parts by Weight

Na2B407.10H20 0.8 10 Citric acid 2.6

Casein 2.0

Esperase 8.0L 0.5

Termamyl 120L 0.3 15 A clay thixo trope detergent composition is prepared for dishwashing, and about 19 parts by weight of the above stabilized enzyme system is added to about 81 parts by weight of the detergent composition to obtain the next dishwashing detergent composition.

Percent by Weight

Deionized water 43.7

Caustic soda solution (50% NaOH) 2.2 25 Sodium carbonate (anhydrous) 5.0

Sodium silicate (47.5% Na20: Si02 ratio = 1: 2.4) 15.74 TPP sodium (substantially an- -30 hydra, i.e. 0-5%, preferably 3% humidity) (Thermphos NW) 12.0 .PTP sodium (hexahydrate) (Thermphos N hexa) 12.0 35 Na2B40 ?. lOf ^ O 0.8 * ^ 35

Citric acid 2.6

Casein 2.0

Esperase 8.0L 0.5

Termamyl 120L 0.3 05 Monostearyl phosphate 0.16 DOWFAX 3B-2 (45% aqueous solution of sodium monodecyl / didecyl- (diphenyl oxide) disulfonate) 0.80

Aluminum stearate 0.20 10 Pharmagel H (Thixotropic clay) 2.0 100.00 EXAMPLE 3

The thixotropic aqueous dishwashing liquid composition of Example 2 containing the stabilized enzyme system of the present invention comprising 0.5 weight percent Esperase 8.0L and 0 was tested. 3 percent by weight of Termamyl 120L, to determine the proteolytic and amylolytic activity after aging at 4 ° C, at room temperature and at 35 ° C for 1, 4 and 8 weeks. The dishwashing detergent composition had a pH of about 11.7. The results obtained are reported in the following table.

Aging temperature Temperature

Aging time 4 ° C ambient 35 ° C

(weeks) 12412 4 '124 30 ------------------------------------------ -----------

Proteolytic activity 77 - 58 - - 51 38 - 32

Amylolytic activity - 50 - - 22 - - 4 -

The stabilized enzyme system of the present invention, consisting of borax-citric acid and *% „36 casein-Esperase and Termamyl ,. not only allows stabilization of the amylase under very unfavorable conditions (the amylase is normally destroyed at pH 9) but also allows an amylolytic-05 activity that observed at very alkaline pH. In fact, the dishwashing detergent composition exhibited amylolytic activity after 5 months of storage at room temperature.

By other tests, it was found that the effectiveness of the above composition on hard residues was greater than that of any commercially available DLAV product, in particular at a low concentration of 5 g / l in the dishwasher.

15 EXAMPLE 4

An aqueous liquid detergent composition is prepared according to the present invention which is suitable for manual washing of dishes and for presoaking, especially very dirty dishes, before machine washing. This composition contains the following ingredients in the proportions indicated.

Percent by Weight

Deionized water 46.1 25 Caustic soda solution (50% NaOH) 2.2

Sodium carbonate (anhydrous) 5.0

Sodium silicate (47.5% Na2Q solution: Si02 = 30 1: 2.4) 15.74 TPP sodium (Thermphos NW) 12.0 TPP sodium (Thermphos N hexa) 12.0

Na2B407.10H20 0.9

Lactic acid 1.8 35 Casein 2.0 "’ * '.

37;

Esperase 8.OL 0.8

DOWFAX 3B-2 monostearyl phosphate 0.16 (45% aqueous solution of sodium monodecyl / didecyl-05 (diphenyl oxide) disulfonate) 0.80

Aluminum stearate 0.50 100.00 The detergent compositions containing a stabilized enzyme dishwashing system of the present invention can also be formulated as powder compositions.

In the above preparation procedure, those skilled in the art can vary the ingredients and their proportions to obtain detergent compositions for washing dishes whose ingredients and proportions are specific.

Claims (23)

1. Aqueous liquid composition for washing dishes, containing a stabilized enzyme system, comprising water, an alkali metal phosphate. 05 as detergency builder salt, an organic surfactant, a boron compound, an acid carboxylic, a protein substance and an enzyme. 2. Composition according to claim 1, characterized in that the boron compound is at least one of borax (Na2B40 ^ .10H20), sodium borate (Na-jBO ^), boric acid and boric oxide. 3. Composition according to claim 1, characterized in that the protein substance is: casein. ; 4. Aqueous liquid composition for washing dishes containing a stabilized enzyme system, comprising, by weight: 35 to 65% of water, 8.1 35% of alkali metal phosphate as detergency builder salt, 0 to 20% sodium silicate, 20 to 5% of an organic surfactant, 0.4 to 2% of a boron compound, 1 to 5% of a carboxylic acid, 1 to 6% of a protein substance and 1 to 6% of enzyme. 5. Composition according to claim 4, characterized in that it comprises 0 to 5% by weight of a thixotropic clay thickening agent. 6. Composition according to claim 4, characterized in that the boron compound is at least one of borax (Na2B40-7 · 10H20), sodium borate (Na3B03), boric acid and oxide boric, and in that the carboxylic acid is an alpha-hydroxy hydroxy carboxylic acid. 7. Composition according to claim 4, characterized in that it comprises, by weight: 40 to 55% of water, 20 to 30% of sodium tripolyphosphate, 35 0 to 5% of an organic surfactant, 0 to 20 % silica-. * V 39 te sodium, 0 to 9% sodium carbonate.,. 0 to 5% of anti-foaming agent, 0.75 to 2.0% of borax (Na ^^ O ^. 10H20), 1.5 to 4.0% of alpha-hydroxy-carboxylic acid, 1, 0 to 4.0% casein and 0.5 to 2.0% enzyme. 8. Composition according to "claim 7, characterized in that the organic surfactant is a sodium (linear tridecyl) benzenesulfonate. 9. Composition according to claim 7, characterized in that the alpha-1 ^ dKS ^ Ksöx ^ liquB 10 acid is at least one of lactic acid, tartaric acid ', citric acid and of their sodium salts. 10. Composition according to claim 7, characterized in that the alpha-hydroxycarboxylic acid is at least one of citric acid and its sodium salt. 11. .A composition according to claim 4; characterized in that it comprises, by weight: 40 to 55% of water, 20 to 30% of sodium tripolyphosphate, 20 0.25 to 5.0% of thixotro pe clay thickening agent, 0.1 to 5 % of anionic surfactant, O to 20% of sodium silicate, 2 to 9% of sodium carbonate, 0.1 to 0.5% of anti-foaming agent, 0.75 to 2.0% of borax (Na2B407.10H20 ), 1.5-4.0% alpha-hydroxycarboxylic acid, 1.0-4.0% casein and 0.5-2.0% enzyme. 12. Composition according to claim 11, characterized in that the anionic surfactant is linear sodium decylsulfonate. 13. Composition according to claim 11, characterized in that the alpha-hydroxy-carboxy-lic acid is at least one of lactic acid, tartaric acid, citric acid and their salts sodium. 14. Thixotropic aqueous composition for / ·. f * * »*? ♦ 40 automatic washing of dishes containing a stabilized enzyme system, comprising, by weight ï 40 to 55% water, 20 to 30% sodium tripolyphosphate, 0.5 to 4.0% thixotropic clay thickener, 2.5 to 20% 05 of sodium silicate, 2 to 9% of sodium carbonate, 0.3 to 2.0% of anionic surfactant, 0.75 to 2.0% of borax (Na2B ^ 0 ^ .10H20 ), 1.5 to 4.0% alpha-hy-droxy-carboxylic acid, 1.0 to 4.0% casein and 0.5 to 2.0% enzyme. '' 15. Composition according to claim 14, characterized in that it contains a long-chain fatty acid metal salt as a physical stabilizing agent, in an amount sufficient to increase the physical stability of the composition. 16. Composition according to claim 15, characterized in that the physical stabilizing agent is aluminum stearate. 17. Composition according to claim 15, characterized in that the physical stabilizing agent is present in a proportion of 0.1 to 2% by weight. 18. Composition according to claim 14, characterized in that the thixotropic thickener is a colloidogenic mineral or organic clay. 19. Composition according to claim 18, characterized in that the clay is a montmorillo-nite, an attapulgite, a hectorite or a smectite. 20. Composition according to claim 14, characterized in that it contains 0.1 to 0.5% by weight of an anti-foaming agent. 21. A method for cleaning soiled dishes, characterized in that it consists in bringing the soiled dishes in contact with the aqueous liquid composition for washing the dishes of claim 1. ^ * r '* "" " * '· 1 »41 22. Method for cleaning soiled dishes in an automatic dishwasher, characterized in that it consists in bringing soiled dishes in contact, in an automatic dishwasher, with an aqueous washing bath in which dispersed an effective amount of the composition of claim 7. 23. Method for cleaning soiled dishes in an automatic dishwasher, characterized in that it consists in bringing soiled dishes in contact, in an automatic dishwasher, with an aqueous washing bath in which · is dispersed an effective amount of the composition of claim 14.