FR2608168A1 - AQUEOUS COMPOSITIONS CONTAINING A STABILIZED ENZYME SYSTEM FOR DISHWASHER CLEANING, AND METHODS OF USING THE SAME - Google Patents

Abstract

THE INVENTION RELATES TO A REINFORCED AQUEOUS LIQUID COMPOSITION CONTAINING A STABILIZED ENZYME SYSTEM, FOR WASHING DISHES. THE STABILIZED ENZYME SYSTEM CONTAINS BORON COMPOUND, ALPHA-HYDROXY-CARBOXYLIC ACID, CASEIN AND AN ENZYME. THIS SYSTEM IS USED IN THE COMPOSITION TO COMMUNICATE TO IT AN EFFECTIVE PROTEOLYTIC AND AMYLOLYTIC ENZYMATIC CLEANING ACTIVITY. THE COMPOSITION CONTAINS ADJUSTING MINERAL DETERGENCE SALTS AND OTHER FUNCTIONAL MINERAL SALTS, THE STABILIZED ENZYME SYSTEM, A DETERGENT AND A METAL SALT OF FATTY ACID AS A PHYSICAL STABILIZER. IN VIEW OF ITS USE FOR AUTOMATIC DISHWASHING, THE COMPOSITION MAY HAVE THIXOTROPIC PROPERTIES BY THE ADDITION OF A THIXOTROPIC CLAY THICKENER. FIELD OF APPLICATION: HOUSEHOLD PRODUCTS FOR DISHWASHING.

Description

French patent application 87.14943 filed

  October 28, 1987, by the Applicant discloses an aqueous liquid laundry detergent composition containing an enzyme stabilizing system comprising a boron compound, an alpha

  hydroxycarboxylic acid, casein and an enzyme.

  French patent application 87.12321 filed

  September 4, 1987 by the Applicant describes a

  thixotropic aqueous composition with clay for washing

  1 st dish, containing aluminum stearate

  as a physical stabilizer.

  The present invention relates to composi-

  enhanced aqueous solutions containing a stabilized enzyme system for dishwashing. The stabilized enzyme system contains a boron compound, an acid

  alpha-hydroxy-carboxylic acid, casein and an enzyme.

  The present invention relates, in particular, to

  Thixotropic aqueous liquid positions to clay for

  the washing of the dishes containing an enzyme system

  Stabilized product which comprises a boron compound, for example

  borax sodium, an alpha-hydroxy carboxylic acid

  that, for example, lactic, tartaric or citric acid

  casein and an enzyme, for example enzymes

  my proteolytic and amylolytic. This invention

  This invention is particularly concerned with detergent compositions containing a stabilized enzyme system.

  for automatic dishwashing, including the

  zyme is stable, physically stable and easy to disperse in a washing medium to effectively clean dishes, glassware, porcelain, etc. Powdered detergent compositions and reinforced aqueous detergent compositions, including

  the thixotropic compositions, for the washing of the

  which are currently available do not contain

  no stabilized enzyme systems.

  The present invention relates to composi-

  enhanced aqueous liquid detergent

  an enzyme for washing dishes, which is

  to clean dishes, glassware,

  wool, utensils, etc. More particularly,

  the invention relates to detergent compositions

  aqueous solutions containing an enzyme for washing dishes, which contain one or more adjuvants

  detergency and which are characterized by their

  you. Automatic dishwashing compositions, also hereinafter referred to as DLAV, generally contain: (1) sodium tripolyphosphate (NaTPP) for

  soften the hard water or-retain the minerals it con-

  and to emulsify and / or "peptise"

res;

  (2) sodium silicate to bring alkali

  nite necessary for effective detergent action and to achieve protection of enamels and patterns of fine porcelain; (3) sodium carbonate, generally considered optional, to increase alkalinity; (4) a chlorine releasing agent to facilitate the removal of small soil stains that

  lead to the formation of water spots and to

  cilitate the elimination of dyeing soiling such as tea and coffee; and (5) an antifoam / surfactant combination to provide the necessary detergency activity and reduce the

  foam, thus increasing the efficiency of the machine.

  See, for example, SDA Detergents in Depth, "Formula-

  Aspects of Machine Dishwashing ", Thomas Oberle os05 (1974) .Cleaning products that approach the compositions described above are for the most part

liquids or powders.

  The use of a chlorine-releasing agent in certain dishwashing compositions

  however, was subject to criticism as this agent

  to react with other chemically active ingredients, particularly the surfactant (see U.S. Patent No. 4,115,308), thereby degrading the thixotropic or suspending agent and reducing

  its efficiency. A characterization of the present

  This is because a chlorine releasing agent is not required in the washing composition of the present invention.

the dishes.

  The formulation of liquid compositions for

  washing dishes containing a stabilizing enzyme

  was a difficult problem. The interest that

  Enzymes can be incorporated into the composi-

  detergents for washing dishes

  comes mainly from the efficiency that the

  proteolytic and amylolytic enzymes in the decom-

  position of the protein and amylaceous substances encountered

  on the dirty dishes and utensils, so that the elimination of

  consumed food such as sau-

  this of meat, eggs, tomato sauce, chocolate and others, during the automatic dishwashing machine. However, enzymatic substances which are suitable for dishwashing compositions, particularly proteolytic enzymes, are relatively expensive. In addition, it is known that enzymes are unstable in the compositions

  aqueous detergents for washing linen

ge.

  In the case of detergent compositions

  washing agents reinforced with a phosphate-type detergency builder, it is known that the

  problem of instability of the enzyme is particularly

  Highly acute. The main cause is that the

  Phosphate detergents have a decisive effect

  stabilizer on the enzymes. In addition, the incorporation of a phosphate-type detergency builder into a liquid dishwashing detergent composition poses an additional problem, namely the

  possibility of forming a stable composition at only one

  the phase; the solubility of sodium tripolyl phosphate,

  for example, being relatively limited in the

  aqueous solutions, and especially in the presence

anionic detergents.

  Stabilization of the enzymes in the compounds

  strongly alkaline detergent formulations is also

  difficult because it is known that the high alkalinity de-

  destroy the enzymes. Although it is possible to

  pH to improve the stability of enzymes,

  it cancels to a certain extent the favorable effect

  detergency builders. The enzyme enzyme system

  balance of the present invention provides stability

  of the enzyme even at relatively high pH,

  only at pH 10-12. The higher pH values, for example pH 10-12, are known to give better detergency and

  they are preferred. A reduction in the pH of the composition

  detergent, for example at pH 7,5-9,5, may increase

  to bring about the stability of the enzyme, but decreases the

  life of the foaming bath and the beneficial effects of the detergency builder, that is, the action

detergent.

6 8 v68

  U.S. Patent No. 4,431,559 discloses that

  a thixotropic composition for self-cleaning

  of the dishware, comprising an aqueous solvent,

  a thickening agent, a source of chlorine, a surfactant

  anionic salts, adjuvant detergency salts and a

  buffer system to stabilize the source of chlorine.

  U.S. Patent No. 3,558,498 discloses that

  a granular detergent composition for washing clothes, containing stabilized enzymes,

  sodium perborate trihydrate, trisodium phosphate

  than anhydrous, anhydrous calcium sulphate and

  soluble or dispersible teins having a molecular weight

  5,000 to 1,000,000, for example casein

  having a molecular weight of 50,000 to 200,000.

  U.S. Patent No. 3,560,392 makes

  a granular detergent composition for washing clothes, containing an organic detergent, a

  Alkaline detergency adjuvant salt, a stabilizing enzyme

  and a stabilizing amount of collagen

  protein having a molecular weight of 5,000 to 250,000.

  U.S. Patent No. 4,238,345 discloses that

  a liquid detergent composition for washing

  laundry, wherein the enzyme is stabilized by the addition of an antioxidant and a hydrophilic polyol having 2 to 6 hydroxyl groups. The patentee declares, at the

  column 1, that calcium salts associated with

  teins and glycerol associated with proteins have been

  used to form stabilizing systems -

  of enzymes in aqueous liquid detergents for the

laundry.

  Patent Application GB-A-2,079,305 discloses

  an aqueous liquid detergent composition

  forcing containing an enzyme for washing laundry, wherein the enzyme is stabilized by a mixture

of a polyol and boric acid.

  The present invention relates to a composition

  A dishwashing polyphosphate-reinforced aqueous liquid solution containing a stabilized enzyme system comprising a boron compound;

  an alpha-hydroxy carboxylic acid, a material

  such as 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

  enzyme and casein in order to block the catalytic sites

  lytics of the enzyme with casein and, simultaneously, to block the structure of the enzyme with the mixture of

  composed of boron and alpha-hydroxy carboxylic acid

than.

  In addition to ensuring very good stability

  proteases, the enzyme stabilizing system of

  the present invention has 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 actual stabilization of amylase activity is surprising because one should expect

  that all amylase activity is destroyed at pH above

less than 9.

  According to the present invention, the washing in

  china of crockery and dirty utensils is ef-

  made by placing the dishes and utensils in contact with a very powerful reinforced aqueous liquid composition for dishwashing, containing the

stabilized enzyme system.

  Aqueous liquid compositions for

  of the present invention are capable of

  to clean satisfactorily dishes and utensils containing both oily and particulate food soils. Moreover, the

2 6081 8

  described compositions can be used for pre-soaking very dirty dishes which must be

  washed in an automatic dishwasher.

  The present invention is based on the discovery

  that a stabilized enzyme system

  taking a boron compound, an alpha hydroxy acid

  carboxylic acid, a protein substance, for example casein, and an enzyme, has a net effect and

  powerful enzyme stabilizer in the composi-

  aqueous liquid solutions for washing dishes.

  In one embodiment, the present invention relates to an aqueous liquid composition for

  the washing of the dishes, including a stable system

  enzyme reading and a suspension of a phosphate-type detergency builder salt in the liquid detergent

  water based anionic surfactant.

  In another embodiment, the present invention

  This invention relates to an aqueous liquid composition

  thixotropic to clay for the washing of the

  1a, comprising an enzyme stabilizing system and a suspension of a phosphate-type detergency builder salt in the aqueous liquid detergent based on

anionic surfactant.

  The Applicant has discovered that an enzyme stabilizing system consisting of a boron compound, an alpha-hydroxy carboxylic acid, a protein substance, for example casein, and an enzyme, exerts an activity. stable enzymatic enzyme for relatively long periods of time in aqueous liquid compositions for dishwashing. The dishwashing compositions of the present invention are physically stable. The aqueous liquid detergent composition of the present invention

  The invention is easy to pour, easy to dose and easy to

  to introduce it in an automatic dishwasher.

  It would be interesting to have an aqueous liquid composition, possibly

  thixotropic with clay, for the washing of the

  the, which contains a stabilized enzyme system and

  optionally a physical stabilizer.

  Therefore, a purpose of this

  The aim is to provide an aqueous liquid composition

  for washing dishes, containing a system

stabilized enzyme system.

  Another object of the invention is to provide a thixotropic aqueous liquid composition in clay for washing dishes, containing a system

stabilized enzyme.

  Still 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, for addition to aqueous liquid compositions, optionally thixotropic, for washing dishes, in order to

  to communicate to said compositions an activity of net-

  efficient enzymatic protection of the proteolytic type and /

or amylolytic.

  Another object of the invention is to

  improve the physical stability of liquid compositions

  a thixotropic aqueous dishwashing gel containing stabilized enzyme systems, incorporating into a clay-thixotropic dishwashing composition a small, effective amount of a metal salt of fatty acid, as a stabilizing agent, for example stearate

  of aluminum, to inhibit the sedimentation of

  in suspension and prevent phage separation.

  his. These and other purposes of the invention

260816 6

  will appear better on reading the description de-

  cut according to the invention and its forms of

  preferred embodiment and are achieved by incorporating

  a stabilized enzyme system in a composi-

  Thixotropic aqueous solution, for example normally in the gel state. In order to improve the physical stability of the dishwashing composition, it may include 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 a stabilized enzyme system containing a 1-5 compound is incorporated. boron, an alpha-hydroxy carboxylic acid, casein and an enzyme, and a stabilizing effect amount of a long chain fatty acid metal salt which is effective to inhibit sedimentation

particles in suspension.

  The present invention relates to a composition

  phosphate-buffered aqueous liquid solution for

  the washing of the dishes, containing a system

  a relatively simple stabilized zyme which comprises a boron compound, an alpha-hydroxy carboxylic acid, a proteinaceous substance, for example casein, and an enzyme. The enzyme stabilizer system ensures the

  stabilization of the active enzymatic ingredient of

  relatively long periods of time, so that small amounts of

of coding enzymes.

  The present invention relates to a composition

  aqueous liquid based on anionic surfactant,

  phosphate reinforced, for the washing of

  stool, containing a stabilized enzyme that can be

  used at high effective pHs of the order of 10-12.

  The present invention also relates to a composition

  powerful and effective way of washing laundry.

  saddle, which does not require the use of a

Chlorinated salt.

  According to a preferred embodiment of the present invention, there is provided an aqueous composition, normally in a gel state, for washing

  automatic dishwashing, with excellent properties

  xotropes, which includes, on a weight basis:

  (a) 8 to 35% of tripolyphosphates of

  cuddles; (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 material

  re detergent action dispersible in water; (e) a thixotropic clay thickener in a proportion sufficient to provide the composition with a thixotropic index of from 0 to 10.0, for example from about 2.5 to 10; (f) 0.5 to 2.0% boron compound;

  (g) 1.5 to 4.0% alpha-hydroxy carboxylic acid

  than; (h) 1 to 4.0% casein; (i) 0.5 to 2.0% enzyme; (j) 5% foam inhibitor; (k) 0 to 8% sodium hydroxide; (1) 0 to 2% of a long chain fatty acid metal salt; and

(m) the rest of water.

  In connection also with this aspect, the invention

  relates to a method for cleaning dishes in an automatic dishwasher with an aqueous bath

  washing agent containing an effective amount of the

  Zl automatic washing liquid detergent assembly (DLLAV) as described above. According to this aspect of the invention, the DLLAV composition can be easily poured into the dispenser cup of the automatic dishwasher and, in just a few seconds, thicken quickly to return to its normal state of gel or paste so as to hold firmly inside the dispenser cup until shear forces are applied again, such as

the dish-washer.

  In accordance with the present invention, the

  The activity of the enzyme is stabilized for a long period of time, so that small amounts of the enzyme provide an 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, a

  alpha-hydroxy carboxylic acid, a protective substance

  such as casein, and an enzyme. The system

  stabilized enzyme is used in composi-

  Anionic type aqueous solutions reinforced with phosphates. Stabilized Enzyme System

  The stabilized enzyme system is preferably

  prepared separately and added to the composition

washing dishes.

  The stabilized enzyme system is preferably

  prepared by a three-stage procedure

pes described below.

  1. A boron compound is added to an acid or salt of alpha-hydroxycarboxylic acid to obtain a

first mixture.

  2. The protein substance, for example casein, is added to an aqueous alkaline solution and the enzyme is added to the aqueous alkaline solution for

get a second mixture.

  3. The mixture of boron compound and alpha-hydroxycarboxylic acid obtained in step 1 is then mixed with the mixture of proteinaceous substance and

  enzyme obtained in step 2 to obtain a premix

  which is the stabilized enzyme system of the pre-

this invention.

  The mixture of step 1 and the mixture of

  Step 2 above can be added each separately.

* rement to the dishwashing composition,

  but the best results of enzyme stabilization

  are obtained by mixing the

  steps 1 and 2, and then adding the premise

  obtained from the washing composition of the

the.

  Although the Applicant does not wish to be bound by any theory of how the stabilized enzyme system works, it is believed that the

  boron compound reacts with alpha-hydroxy-car-

  boxylic acid or alpha-hydroxy-polycarboxylic acid to form a boric acid ester. The boric acid ester is supposed to react on the enzyme and block its

  structure in the active configuration by protecting it

  thus, against denaturing. The substance

  is supposed to block the catalytic sites of the enzyme and thereby prevent the digestion of other

  enzyme molecules during product storage.

  The stabilized enzyme system comprises: - a boron compound, for example borax, in an amount of 0.4 to 2.5, preferably 0.75 to 2.0 and more preferably 0.9 to 1.2, parts by weight; an alpha-hydroxycarboxylic acid, in an amount of 1 to 5, preferably 1.5 to 4.0 and more preferably 1.8 to 3.6, parts by weight;

  a protein substance, for example the case

  in an amount of from 1 to 6.0, preferably from 1 to 4.0, for example from 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, par-

by weight.

  The weight ratio of alpha-hy-

  hydroxycarboxylic compound to the boron compound may be

  7: 1 to 1: 1, preferably 4: 1 to 1: 1 and more preferably

re from 3: 1 to 2: 1.

  The weight ratio of the protein substance

  eg casein, to the enzyme can be

  from 8: 1 to 1: 1, preferably from 4: 1 to 1: 1 and more preferably

core from 4: 1 to 2: 1.

  A preferred stabilized enzyme system of

  the present invention comprises the following constituents:

in the quantities indicated.

  Parts by Weight Borax (Na2B407, 10H20) 0.75 to 2.0 Alpha-hydroxycarboxylic acid 1.5 to 4.0 Casein 1.0 to 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 to 90 to 70 parts by weight of

  detergent composition, preferably from 15 to 25 parts

  by weight of mtèemy st & ry F'r 85 to 75 prtis in "icb dea m -itin dbe t, and micx e from 15 to 20 prtien pi-dt

  85 to 80 parts by weight of

  detergent. The stabilized enzyme system is added to the dishwashing detergent composition in such a way that the percentages of

  the active ingredients of the enzyme-stabilized system

  bilized in the detergent composition are equivalent

  slow to the parts by weight mentioned above of

  active ingredients in the stabilized enzyme system

See.

  A detailed description of the system

  stabilized zyme is presented in the application for

vet French 87.14943 above.

  The stabilized enzyme system of the present

  The invention can be used in aqueous liquid dishwashing compositions in aqueous thixotropic liquid compositions.

  for washing dishes and in

  granular or powdered detergents for washing dishes.

  Stabilized enzyme systems of the present invention

  invention are, in a preferred form of

  addition to aqueous liquid compositions

  its thixotropes for washing dishes.

  Alpha-Hydroxy-Carboxylic Acids The alpha-hydroxy-carboxylic acids that can be used in the present invention are organic carboxylic acids having from 3 to 8

  carbon atoms, including 1 to 3

  boxyl, and 1 to 3 hydroxyl groups.

  Preferred carboxylic acids are alpha-hydroxycarboxylic acids having 3 to 6 atoms

  of carbon, including 1 to 3 carboxylic acid groups

  that, and 1 to 2 hydroxyl groups. Alpha-hyalic acids

  Suitable hydroxycarboxylic acids include: malic acid (OCCEbC2rOOH), tartaric acid (HOOCCHOHCHOHCOOH), lactic acid (HOOCCHOHCH3) and

  citric acid (HOOCCH2C (OH) COOHCH2COOH).

  The preferred alpha-hydroxy carboxylic acids are

  tartaric, lactic and citric acids. The acid

  is the most appreciated. Alpha-hydroxy acids

  carboxylic acids can be used as such or in the form of their alkali metal salts, such as

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, being added to the water, form

  boric acid or an alkali metal salt of boric acid

  than. Boron compounds that can be used include boric acid, boric oxide or a

  alkali metal borate. Suitable borates of

  Alkaline levels are ortho-, pyro- and metaborates

  sodium and potassium, polyborates and

  rax (Na2B4O7.10H2O). The preferred boron compounds are boric acid, sodium borate (Na3BO3) and

borax (Na2B4O7.10H2O).

enzymes

  Enzymes to incorporate into the composi-

  for washing the dishes of this

  vention may be proteolytic enzymes or

  amylolytics or mixtures thereof. The

  proteolytic zymes in this

  include the various commercial preparations

  in the form of liquid, powder or paste, which have been adapted for use in detergent compositions. Although the incorporation of the enzyme into the composition is more convenient in liquid form,

  enzymes in paste form have been shown to be useful

  the. Appropriate enzyme preparations under

  liquid include "Alcalase" and "Esperase" sold by Novo Industries, Copenhagen, Denmark; "Maxatase"

  and "Maxacal" sold by Gist-Brocades, Delft, Netherlands

  Low; and "Optimase" sold by Miles Kali Chemie. of the

  appropriate proteolytic enzymes include the sub-

  tilisin, bromelain, papain, trypsin and

  pepsin. Suitable enzymes include a

  liquid tetase and a liquid amylase. Enzymes are

  preferably used in the form of their solutions.

  A preferred enzyme is Esperase8L in the form of a

  solution. Appropriate preparations of alpha-amylase

  are in liquid form are those sold by Novo

  Industries and Gist-Brocades under the trademarks of

  that respective "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 enzyme

  is Esperase8.OL because of its strong activity

  at 60 C and its low temperature activity

  room. In addition, Esperase 8.OL is stable at high pH

  vé, which allows a higher pH in the product

  final and a better-detergent action.

  Protein Substance One of the constituents of the enzyme stabilizing system of the present invention is a substance

  protein, for example casein. Substances

  are used in the form of their hydro-

  soluble alkali metals (eg sodium or potassium) and / or are dispersed in a medium

  aqueous solution to which the enzyme is added.

  Proteins that are soluble or dispersible

  Sand in water is used here in an amount effective to stabilize the enzymes. Examples of

O68 16

  proteins that are soluble or dispersible in water and that are usable here include casein

  (average molecular weight of 50,000 to 200,000); Wil-

  its Protein WSP-X-1000 (a solubilized collagen having an average molecular weight of about 10,000) and

  Wilson's Hydrolysate Cosmetic 50, both commercially

  by Wilson's Pharmaceutical & Chemical Company; and Collagen Hydrolyzate Cosmetic 50, available from Maybrook, Inc. A preferred casein protein is sold under the trade name "Caseinate

  Sodium "by Bridal (France) or Dena, A.G. (R. F. A.).

  Sodium Caseinate is a mixture of several

  caseins of different molecular weights. The prote-

  Ines, for example casein, are normally

  in the form of powders. Proteins such as casein have the structure of long chains

  chemical. In powder form, the chains are

  folded on themselves and form hydro-

  which maintain the protein in a global form

  lary. Detangling or denaturing the protein involves breaking these bonds to form a looser, less orderly structure. The proteins

  can be denatured by boiling

  and by the use of acids, alkalis and various detergents. The untangled or denatured proteins are

  more easily digested by enzymes and produced

  therefore, a better stabilizing effect,

  that is, 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 achieve the

  stabilization of enzymatic activity.

  Detergent Composition for Dishwashing

  In general, the effectiveness of

2X608O16

  thixotropic aqueous positions in clay for the

  The crockery is related to: (a) alkalinity, (b) solubility in the washing medium, and (c) foam inhibition. 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 most preferably at least about 11.5. At relatively lower pH values, the detergent product for

  washing of dishes is too viscous, that is,

  is almost solid, so it's not easy to

  Under shear forces at the intensities where they are generated in the distributor bucket under normal operating conditions of the machine. In a nutshell, the composition loses much, if not all, of its character

  thixotropic. 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 needed here because it acts as a buffer that helps maintain the desired level of pH. A

  However, excess carbonate is to be avoided because

  resulting in the formation of acicular carbonate crystals, which would compromise the stability,

  thixotropy and / or detergency of the DLLAV product, and

  so that its ability to be dispensed from, for example, vials in compressible tubes. Another function of caustic soda (NaOH) is to neutralize

  the phosphoric acid ester type foam inhibitor

  that or phosphonic, if present. Proportions

  Typical NaOH and sodium carbonate compositions 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 alkalinity

2 60816

  can be provided by NaTPP and Silicon

  sodium cate. Sodium silicate can be used

  in proportions of 0 to 20 percent by weight,

  preferably 2.5 to 20 percent by weight and more preferably

OS core 5 to 15 percent by weight.

  NaTPP is used in the DLLAV composition in amounts of about 8 to 35 percent by weight, preferably about 20 to 30 percent by weight. NaTPP can be anhydrous or hydrated, which includes stable hexahydrate o degree of hydration

  of 6 corresponds to approximately 18% by weight of water or

  vantage. In fact, given the stability of

  hexahydrate, the presence of a little hydrata-

  tion is very effective in that it serves, thinks

  to form stable hexahydrate seeds which

  promote the hydration and solubilization of

  remaining particles of NaTPP. If only hexahydrate is used, the detergent product may be too much

  liquid and have little, if any, character

  thixotropic. On the other hand, if only anhydrous NaTPP is used, the product may in some cases be too thick and therefore inappropriate. Particularly preferred DLLAV compositions are obtained, for example, when using a weight ratio of

  NaTPP (anhydrous to hexahydrate) from 0.5: 1 to 2: 1,

  their nearest 1: 1 being especially preferred.

  Rees. Inhibition of the foam is important to increase the efficiency of the washing machine the

  dishes and minimize the destabilizing effects

  can occur because of the presence of excess foam in the water during use. The foam can be sufficiently reduced by a choice

  the type and / or quantity of material

  tersive, this component being the main producer

  of foam. The degree of foaming also depends on

  that little of the hardness of the wash water contained in

  the machine, so that an adequate adjustment of the

  portions of NaTPP, which exerts a softening effect

  water, can help to achieve the desired degree of

  bition of the foam. However, we can at best

  Closes a depressant or foam inhibitor in cases where a low foaming DLLAV product is desired. Particularly effective foam inhibitors are the alkyl esters of phosphonic acids having the formula:

HO- P - R

|

  OR provided, for example, by BASF-Wyandotte (PCUK-PAE), and

  especially the acidic alkyl esters of phosphoric acid

corresponding to the formula:

HO- P - OR

  ! OR provided, for example, by Hooker (SAP) and Knapsack (LPKn-158), or one of the R groups or both in

  each type of ester may represent independently

  C12-C20 alkyl groups. Mixtures of esters of the two types or mixtures of mono- and diesters of the same type may be used. A particularly preferred foam inhibitor is a mixture of acid phosphates of mono- and di-C16-C8 alkyls.

  such as a 1.2 / 1 mixture of monohydric acid phosphates

  stearyl / distearyl (Knapsack). If used, typical amounts of suds inhibitor in the composition are from 0.1 to 5 percent by weight, preferably from about 0.1 to 0.5 percent by weight,

  the weight ratio of the detergent component (d) to

  Foam hibitor (j) being generally understood

  in the range of about 10: 1 to 1: 1 and preferably

  from about 4: 1 to 1: 1. Other anti-foam agents that can be used include, for example,

known silicones.

  Sodium silicate, which gives alkalinity

  and protects the hard surfaces, such as the enamels and patterns of fine porcelain, is

  used in the composition in a proportion

  in the range of about 2.5 to 20 percent by weight, preferably about 5 to 15 percent by weight. Sodium silicate is usually added as an aqueous solution, the ratio of which

  Na 2 O: SiO 2 is preferably from about 1: 2.2 to 1: 2.8.

  At this point, it should be noted that most of the

  components of the present composition, especially NaOH, the foam inhibitor and the thickener of

  thixotropy, are also often added under

  of a previously prepared dispersion or aqueous solution. The detersive materials useful herein are water-dispersible surfactants of the compound types

  organic anionic, amine oxide, phosphine oxide

  ne, sulfoxide or beta. Anionic surfactants

  are preferred. Surfactants, for example surfac-

  anionic cells, are used in

  in the range of about 0.1 to 5%, preferably

  from about 0.3 to 2.0%. Particular surfactants

  Most preferred herein are the mono- and / or di-C8-C14 alkyl- (diphenyl) mono- and / or linear or branched alkali metal disulfates available commercially, for example under the names

  DOWFAX (Registered Trade Mark) 3B-2 and DOWFAX 2A-

  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

  is lying. In addition, the surfactif should be compatible

  with the other ingredients of the composition. On au

  suitable surfactants include alkylsulfates

  primary alkyl groups, alkylsulphonates and alkylarylsulphonates, and the alkyl group alkyl sulphates

  secondary. Examples are (C10-alkyl)

  C18) sodium sulfates such as sodium dodecyl sulfate and sodium (sodium tallow alkyl) sulfate; sodium C10-C18 alkanesulfonates such as sodium hexadecyl-1-sulfonate; and the alkyls

  C12-C18) sodium benzenesulfonates such as

  sodium decylbenzenesulfonates. The corresponding potassium salts can also be used. of the

  examples of suitable alkylsulphonates are (al-

  primary kyl in C10-C18) sodium sulfonates and

  potassium, the C10-C15 normal primary alkyl sulphate

  sodium fonates being preferred.

  As other surfactants or detergents

  the amine oxide surfactants have typically been

  R2R N = O, in which each R represents a lower alkyl group, for example methyl, and R1 represents a long-chain alkyl group having from 8 to 22 carbon atoms, for example a lauryl, myristyl, palmityl or cetyl. the

  Instead of an amine oxide, it is possible to use a surfactant

  tif of the corresponding type R2R phosphine oxide 1PO or sulfoxide RRlSO. Betaine surfactants

  typically have the structure R2R1N-R'COO-, in which

  R 'represents a lower alkylene group having 1 to 5 carbon atoms. Specific examples of these surfactants are lauryl dimethyl amine oxide, myristyl dimethyl amine oxide,

  corresponding phosphine and sulphoxides, and

  corresponding products, including dodecyl acetate

  dimethyl ammonium, tetradecyl-diethyl pentaxate

  ammonium, hexadecyl dimethyl ammonium hexanoate,

  etc. To ensure biodegradability, the groups

  kyle of these surfactants must be linear, and

such compounds are preferred.

  Surfactants of the above types, all well known in the art, are for example described in

  U.S. Patent Nos. 3,985,668 and 4,271,030.

  Thixotropic thickening agents, that is,

  ie thickening or suspending agents

  which confer thixotropic properties on a

  aqueous place, are known in the art and can be organic or mineral, water-soluble, dispersible

  in water or colloidogens, and monomers or polymeric

  res, and they must obviously be stable in these

* compositions, particularly with regard to the strong alkalinity

  nity. Thixotropic thickeners which are particularly

  particularly preferred generally include

  colloidogenic mineral clays of the

  te and / or attapulgite. We can also use

  organic clays as thixotropic thickeners.

  These materials have been used generally in amounts of about 1.5 to 10, preferably

  2-5 per cent by weight to confer the properties

  thixotropic elements and the character of plasticity Bin-

  gham desired DLLAV compositions described in the previous applications of the Applicant GB-2 116 199A

and -2 140 450A.

  According to the present invention, proportions of the colloidogenic mineral clays of

  smectite and / or attapulgite types included in the

  from about 0.25 to 5%, preferably from 0.50 to

  4.0%, in particular 1.0 to 3%, are generally sufficient

  to obtain the thixotropic properties and the

  Bingham plasticity character desired. In addition,

  the amounts of thixotropic agent may be employed when used in conjunction with a salt

  metal fatty acid stabilizer

physical situation.

  Smectite-type clays include the various varieties of montmorillonite (bentonite),

  hectorite, attapulgite, smectite, saponite and others.

  Montmorillonites are preferred and are available

  under trademarks such as Thixogel (Registered Trade Mark) N 1 and Gelwhite (Trade Mark) GP, H, etc., at Georgia Kaolin Company; and ECCAGUM (Trade Mark) GP, H, etc., at Luthern Clay Products. Attapulgites include the materials available under the trademark Attagel (Registered Trade Mark), ie Attagel 40, Attagel 50 and Attagel 150,

  at Engelhard Minerals and Chemicals Corporation.

  Mixtures of the smectite and attapulgite types in weight ratios of 4: 1 to 1: 5 are also useful

  right here. Thickening or suspending agents

  The foregoing are well known in the art and are described, for example, in U.S. Patent No. 3

  985 668 referred to above. Abrasives or polishing agents

  smoothing should be avoided in the compositions

  DLLAV, because they can damage the surface of the

fine saddle, crystal, etc.

  The proportion of water contained in these constituents

  obviously must not be excessive

  to generate too low viscosity and too much

  fluidity, nor insufficient to generate too high viscosity and too low flowability, the thixotropic properties being in one case or other reduced or destroyed. This

  proportion is easily determined by experimentation.

  in any particular case, and is generally in the range of about 65 percent by weight, preferably about

  40 to 55 percent by weight. It is also necessary to

  whether the water is deionized or softened.

  Unless otherwise indicated, the description

  The DLLAV product conforms generally to that of the compositions described in the

  Patent GB-2,116,199A and 2,140,450A of the Applicant.

  The DLLAV products of the earlier applications GB-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

  LEMENT. These compositions exhibit a high viscosity

  lower shear rate and a viscosity

  lower head with high shear rate; the results

  States indicating that fluidification and gelation

  effective effects occur largely indoors

  limits of the range of shear rates

  countered in standard automatic dishwashers.

  In practical terms, this translates into better payout and implementation characteristics,

  and less leakage in the distribution bucket

  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 from about 10,000-30,000 mPa.s to about 3,000-7,000 mPa.s, respectively, as measured at room temperature. ambient by means

260.81686-

  of a Brookfield LVT viscometer after 3 minutes using a N 4 spindle. Shear rate

  7.4 s-1 corresponds to a spindle speed of approx.

  3 rpm. An increase of about 10 times in the shear rate results in a reduction of about 3 to 9 percent of the viscosity. With the DLAV gels of

  the prior art, the corresponding reduction of

  cosity was only about 2 times. In addition, with

  these compositions, the initial viscosity noted at

  about 3 rpm was only about 2,500 to 2,700

  mPa.s. These compositions of previous applications pre-

  quoted thus show thresholds of fluidification

  at lower shear rates and a higher

  significantly higher in terms of incremental increase in shear rate as a function of incremental decay in viscosity. This property of the DLLAV products of the aforementioned prior applications is summarized by a thixotropy index (IT) which is the ratio of apparent viscosities to

  3 rpm and 30 rpm. The compositions of these

  previous orders have an IT of 2 to 10. The composi-

  DLLAV trials have shown a massive and rapid return to the consistency of the state of rest

  upon cessation of shear force.

  French patent application 87.12321 men-

  above, is based on the discovery according to the-

  what physical stability, that is to say the resistance

  phase separation, sedimentation,

  etc., liquid aqueous DLAV compositions of

  patent applications GB-2 116 199A and -2 140 450A can

  be significantly improved, without affecting harmful-

  and in some cases by improving their

  rheological properties, adding to these compositions

  a small but effective amount of a metal salt

  than a long-chained fatty acid.

  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

  often be increased 2-3 times by incorporating

  as little as 0.2% or less, for example 0.16%, of the fatty acid metal salt

  stabilizing. At the same time, the physical stability

  that can be improved to such an extent that

  near a long period of time, twelve weeks or

  more, in extended temperature ranges

  from almost freezing up to 40 C or higher, the compositions containing the metal salts of

  stabilizing fat does not undergo any separation

serviceable of phases.

  The preferred long-chain fatty acid metal salts are those of the aforementioned application 87.12321. Metal salts of acids

  appropriate fatty acids are the metal salts of

  higher aliphatic fats having about 8 to about 22 carbon atoms, preferably about 10 to 20 carbon atoms, and most preferably

  particular about 12 to 18 carbon atoms, including

  took the carbon atom from the carboxyl group of the acid

  fat. The aliphatic radical can be saturated or unsaturated

  tured and it can be straight or branched. Straight chain saturated fatty acids are preferred. Mixtures

  fatty acids can be used, such as those

  from natural sources, such as tallow fatty acid, coconut fatty acid, soy

  etc., or synthetic sources that are available

  of industrial manufacturing processes.

  Thus, examples of the fatty acids from which the metal salts can be prepared

  stabilizers include, for example, decahydrate

  noic, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid, fatty acid soybeans, mixtures of these acids, etc. Stearic acid and mixtures

fatty acids are preferred.

  Preferred metals are polyvinyl

  slow ones such as magnesium, calcium, aluminum

and zinc.

  Many of these metallic seis are available

  in commerce. For example, aluminum salts

  are available in the form of three residues

  acid, for example aluminum stearate under

  Aluminum (Al) (C17H35COO) 3. Salts with a single acid residue, eg monostearate

  Al (OH) 2 (C17H35COO) aluminum, and the two-fold salts

  acid residues, for example aluminum distearate Al (OH) (C17H35C00) 2, and mixtures of two or three salts with one, two and three acid residues, can be used for metals which, such as , have valence

  +3, and salt mixtures with one and two acid residues

  can be used for metals which, such Zn,

have the valence +2.

  The polyvalent salts of fatty acids that are preferred as stabilizing agents are calcium stearate, that is calcium distearate, magnesium stearate, that is magnesium distearate,

  aluminum stearate, that is to say the tristearate of

  luminium, and zinc stearate, that is to say the di-

zinc stearate.

  Naturally, the use of fatty acids

  The stabilizing agents, because of their well-known low toxicity, offer a particular advantage for DLLAV compositions, as well as for all others.

  applications in which the composition of the invention

  between or is likely to come into contact with objects used to handle, preserve or serve food products or is otherwise likely to come into contact with or be consumed by humans or animals. In this

  calcium stearate, that is the distal

  calcium arate, and magnesium stearate, is it

  that is magnesium distearate, are particularly

  are preferred because they are food additives

  inoffensive in general.

  The proportion of metal salts of acids

  stabilizing fats suitable for the improvement

  the desired stability of physical stability depends on

  such as the nature of the fatty acid salt, the nature of

  re and the proportion of thixotropic agent,

  detergent, mineral salts, including TPP, and other ingredients of the DLLAV product, as well as

  conditions laid down for the storage and trans-

  Harbor. However, in general, proportions of the fatty acid metal salt stabilizers are from about 0.2 to 2%, preferably from about 0.5 to 1.0%, and most preferably from about about 0.5 to 0.8%, provide long-term stability and absence of phase separation at rest or during transport at low and high temperatures, as required for an acceptable product

from the commercial point of view.

  Depending on the proportions and types of physical stabilizers and thixotropic agents, the addition of the metal fatty acid salt not only increases physical stability but also provides

  a simultaneous increase in the apparent viscosity.

  Ratios of fatty acid to thixotropic agent ranging from about 0.08 to 0.4 percent by weight of fatty acid for about 1.3 to 2.5 percent by weight of agent.

  thixotropy, are usually sufficient to

  these advantages at the same time and, consequently, the greatest preference is given to the use of these

ingredients in these reports.

  According to one of the processes for the manufacture of these compositions, all the inorganic salts, that is to say the carbonate (if it is used), the silicate and the

  tripolyphosphate, in the aqueous medium. The thick agent

  <if used) is added just before the stabilized enzyme system. The foam inhibitor (if used) is previously prepared as an aqueous dispersion, as is the thickening agent. The foam inhibitor dispersion, the

  caustic soda (if used) and the

  The crystals are first mixed at elevated temperature to form an aqueous solution (deionized water), then cooled, with stirring from start to finish.

  the operation. Surfactant, the stabi-

  reading and the dispersion of thickening agent 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 about 20 weight percent, preferably about 30 to about weight percent, in the composition. The stabilized enzyme system is generally about 15 to 25 parts by weight, preferably 15 to 20 parts by weight.

by weight, of the composition.

  Another method for mixing the ingredients

  of DLLAV compositions is to train everything

  first a mixture of water, the inhibitor of

  (if it is used), detergent,

  physical stabilization (if it is used), for example

  a fatty acid salt, and thixotropic agent

  (if it is used), for example a clay. These

  The ingredients are mixed together under high shear conditions, preferably starting at room temperature, so that

  uniform persion. The remaining ingredients are incor-

  pores to this premix under mixing conditions

  at low shear. For example, the quantity required

  The remaining premix is introduced into a low shear mixer, and 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), metal tripolyphosphate

  alkaline (anhydrous or containing not more than 5% water), hy-

  sodium hydroxide and finally a stabilized enzyme system

  See. Other conventional ingredients may be included in these compositions in small proportions,

  generally less than 3 per cent by weight

  eg perfume, hydrotropic agents

  such as benzene-, toluene-, xylene-, and cumene-

  sodium sulfonates, preservatives,

  dyes and pigments, etc., all being obviously

  stable with respect to high alkalinity (

  common property to all components). Subjects

  Particularly preferred dyes are phthalate

  chlorinated cyanines and aluminosilica polysulfides

  who respectively communicate pleasant tidings

  your green and blue. TiO2 can be used for white

  chir or neutralize degraded shades.

  The liquid DLAV compositions of the present

  The invention is easily used in a known manner for washing dishes, cooking utensils, etc.

  in an automatic dishwasher equipped with a

  suitable scorer of detergent, in an aqueous bath

  washing agent containing an effective amount of the

sition.

  Although the invention has been described in

  particularly as regards its application to

  For the automatic washing of dishwashing agents, those skilled in the art will readily realize that the advantages obtained by the addition of the stabilized enzyme system are equally applicable to aqueous liquid compositions. and to the powder compositions for washing

dishes.

  The invention can be practiced in a variety of ways and a number of particular embodiments will be described in

  illustrative purposes in the examples below

  the quantities and proportions are expressed by weight relative to the weight of the composition, except

otherwise stated.

EXAMPLE 1

  In accordance with the present invention,

  a stabilized enzyme system by proceeding according to

the following procedure.

  (1) 12.6 grams of sodium borate (Na3BO3) is added to 56.1 grams of tartaric acid in 90

  grams of water, while stirring. We neutralize the

  to about pH 7 with 56.1 grams of NaOH

(50% solution).

  (2) 60 grams of casein, supplied by Bridel, was added to 270 grams of water containing 1.8 grams of NaOH with stirring and heating. After complete dissolution, 15 grams of Esperase 8.OL are added at 500 ° C. and 9 grams of Termamyl 120L are added to the mixture.

  room temperature, to obtain a casein-

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

  the stabilized enzyme premix of the present invention.

  tion. The entire premixed stabilized enzyme system, i.e., about 570.6 grams, may be incorporated into an aqueous liquid dishwashing composition or into a solid state.

liquid aqueous liquid composition

  clay xotrope h.Our 1 e 1 a v a g e - dishwashing so

  to obtain about 3000 g of composition for washing

  age of the dishes, the quantity in which the

  tibants of the stabilized enzyme system of the present

  invention are present in the following proportions

your.

  Weight percent Na3BO3 0.4 Tartaric acid 1.9 Casein - 2.0 Esperase 8.OL 0.5 Termamyl 120L 0.3 Dishwashing compositions which contain the stabilized enzyme system of the present invention prove effective for cleaning

  dirty dishes, even in the absence of

containing active chlorine.

EXAMPLE 2

  According to the procedure of Example 1, a stabilized enzyme system containing

the following ingredients.

Parts in Weight Na2B407.1OH20 0.8

N2B4 7 '2

  Citric acid 2,6 Casein 2.0 Esperase 8.OL 0.5 Termamyl 120L 0.3

  A thixo-detergent composition is prepared

  a clay trope for washing dishes, 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 composition

  detergent for washing the following dishes.

  Weight percent Deionized water 43.7 Caustic soda solution (50% NaOH) 2.2 Sodium carbonate (anhydrous) 5.0 Sodium silicate (47.5% Na 2 O: SiO 2 solution)

1: 2,4) 15,74

TPP sodium (substantially

  hydrate, ie 0-5%, preferably 3% moisture) (Thermphos NW) 12.0 TPP sodium (hexahydrate) (Thermphos N hexa) 12.0 Na2B407.1 20 0.8 Citric acid 2,6 Casein 2.0 Esperase 8.OL 0.5 Termamyl 120L 0.3 Monostearyl phosphate 0.16 DOWFAX 3B-2 (aqueous solution of Na monodecyl / didecyl- (diphenyl) disulfonate) 0.80 Pharmagel H Aluminum Stearate 0.20 (Thixotropic Clay) 2.0, 00

EXAMPLE 3

  The aqueous thixotropic dishwashing liquid composition of Example 2 containing the stabilized enzyme system of the present invention comprising 0.5 percent by weight of Esperase 8 was tested. OL and 0, 3 percent by weight of

  Termamyl 120L, to determine the proteolytic activity

  lytic activity and amylolytic activity after aging.

  at 4 C, at room temperature and at 35 C

  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 TeMps aging 4 C ambient 35 C (weeks) 1 2 4 1 2 4 '1 2 4 Proteolytic activity 77 - 58 - - 51 38 - 32

  Amylolytic activity - 50 - - 22 - - 4 -

  The stabilized enzyme system of the present

* the invention, composed of borax-citric acid and casein-Esperase and Termamyl, not only allows stabilization of amylase under very unfavorable conditions (the amylase is normally destroyed

  at pH 9) but also allows an amylolytic activity

  than observed at very alkaline pH. In fact, the composi-

  detergent for washing the vaibelle

  feasted amylolytic activity after 5 months of

  storage at room temperature.

  By other tests, it has been found that

  the effectiveness of the above composition on the

  sidus hard was greater than that of any

  commercially available DLAV duit, including

  a low concentration of 5 g / l in the washing machine

saddle.

EXAMPLE 4

  In accordance with the present invention,

  an aqueous liquid detergent composition suitable for manual dishwashing and pre-soaking, especially very dirty dishes,

  before washing in the machine. This composition

  keeps the following ingredients in

  diquées. Weight Percentage Deionized Water 46.1 Caustic Soda Solution (50% NaOH) 2.2 Sodium Carbonate (Anhydrous) 5.0 Sodium Silicate (47.5% Na 2 O: SiO 2 =

1: 2,4) 15,74

  Sodium TPP (Thermphos NW) 12.0 Sodium TPP (Thermphos N hexa) 12.0 Na2B407. 10H20 0.9 Lactic acid 1.8 Casein 2.0 Esperase 8.OL 0.8 Monostearyl phosphate 0.16 DOWFAX 3B-2 (aqueous solution

at 45% monodecyl / didecyl

  (Na (diphenyl) disulphonate) 0.80 Aluminum stearate 0.50. 00 The detergent compositions containing

  stabilized enzyme system for washing the vessel

  saddle of the present invention may also

  be formulated as powder compositions.

  In the procedure of preparation hereinafter

  above, those skilled in the art can vary the

  and their proportions to obtain composi-

  detergent detergents for dishwashing

  the ingredients and proportions are specific.

Claims (23)

  1. Aqueous liquid composition for washing   dishwashing, containing a stabilized enzyme system   comprising water, an alkali metal phosphate   as a detergency builder, an organic surfactant   that a boron compound, a carboxylic acid, a protein substance and an enzyme.   2. Composition according to claim 1, characterized in that the boron compound is at least one borax (Na2B407.10H20), sodium borate   (Na3B03), boric acid and boric oxide.   3. Composition according to claim 1, characterized in that the protein substance is casein.   4. Aqueous liquid composition for the la-   a dish containing a stabilized enzyme system comprising, by weight: 35 to 65% water,   8 to 35% of alkali metal phosphate as the ad-   detergent builder, 0 to 20% sodium silicate,   0 to 5% of an organic surfactant, 0.4 to 2% of a compound   boron, 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   a thixotropic clay thickener.   6. Composition according to claim 4, characterized in that the boron compound is at least one of borax (Na2B407 .10H20), sodium borate (Na3B03), boric acid and boric oxide,   and in that the carboxylic acid is an alpha-   hydroxy-carboxylic acid. 7. Composition according to claim 4, characterized in that it comprises, by weight: 40 to% of water, 20 to 30% of sodium tripolyphosphate,   0 to 5% of an organic surfactant, 0 to 20% of 2608U 1 6   sodium tetra, 0 to 9% sodium carbonate, 0 to 5%   of antifoaming agent, 0.75 to 2.0% borax (Na2B407.   H 2 O), 1.5 to 4.0% of alpha-hydroxy carboxylic acid   1.0 to 4.0% casein and 0.5 & 2.0% enzyme.   8. Composition according to claim 7, characterized in that the organic surfactant is a   (linear tridecyl) sodium benzenesulfonate.   9. Composition according to Claim 7, characterized in that the alpha-hydroxyalkylcisyl acid is at least one of lactic acid, tartaric acid, citric acid and their salts. sodium. 10. Composition according to claim 7,   characterized in that the alpha-hydroxycarboxylic acid   lique is at least one of the citric acid and its sodium salt.   11. The composition of claim 4; characterized in that it comprises, by weight: 40 to% of water, 20 to 30% of sodium tripolyphosphate,   0.25 to 5.0% thixotropic clay thickener   pe, 0.1 to 5% of anionic surfactant, O to 20% of   sodium halide, 2 to 9% sodium carbonate, 0.1 to 0.5% antifoaming agent, 0.75 to 2.0% borax   (Na2B407, 10H20), 1.5 to 4.0% of alpha-hydroxy acid   carboxylic acid, 1.0 to 4.0% casein and 0.5 to 2.0% enzyme. 12. Composition according to claim 11, characterized in that the anionic surfactant is the   decylsulfonate-linear sodium.   13. Composition according to claim 11,   characterized in that the alpha-hydroxycarboxylic acid   lique is at least one of lactic acid,   tartaric acid, citric acid and their sodium salts. 14. Thixotropic aqueous composition for automatic dishwashing containing a stabilized enzyme system comprising, by weight: 40 to 55% water, 20 to 30% sodium tripolyphosphate, 0.5 to 4.0% d thixotropic clay thickener, 2.5 to 20% sodium silicate, 2 to 9% sodium carbonate, 0.3 to 2.0% anionic surfactant, 0.75 to 2.0% of   borax (Na2B4O7.10H2O), 1.5 to 4.0% of alpha-hy-   hydroxycarboxylic 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 metal salt   of long-chain fatty acid as a stabilizing agent   a quantity sufficient to increase the   be the physical stability of the composition.   16. Composition according to Claim 15,   characterized in that the physical stabilizing agent what is aluminum stearate.   17. Composition according to Claim 15,   characterized in that the physical stabilizing agent   that 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 mineral or organic colloidal clay.   19. The composition of claim 18,   characterized in that the clay is a montmorillon   nite, attapulgite, hectorite or smectite.   20. Composition according to claim 14, characterized in that it contains 0.1 to 0.5% by weight. weight of an antifoaming agent.   21. A method for cleaning soiled dishes, characterized in that it consists in putting the   dirty dishes in contact with the liquid composition   aqueous solution for washing dishes of the cation 1. 2 60816   22. A method for cleaning soiled dishes in an automatic dishwasher, characterized in that it consists in putting the dirty dishes in contact, in an automatic dishwasher, with an aqueous washing bath in which is dispersed a   effective quantity of the composition of the 7.   23. A method for cleaning soiled dishes in an automatic dishwasher, characterized in that it consists in putting the dirty dishes in contact, in an automatic dishwasher, with an aqueous washing bath in which is dispersed a   effective quantity of the composition of the 14.