FR2546902A1 - ONE-PHASE LIQUID ANIONIC DETERGENT COMPOSITION COMPRISING A DETERGENT ADJUVANT AND CONTAINING STABILIZED ENZYMES AND A WASHING METHOD USING THE SAME - Google Patents

Abstract

THE INVENTION RELATES TO A SINGLE-PHASE LIQUID ANIONIC DETERGENT COMPOSITION WITH ADJUVANT AND CONTAINING ONE OR MORE ENZYMES. THIS COMPOSITION CONSISTS OF: A. APPROXIMATELY 8 TO 20 BY WEIGHT OF ONE OR MORE SURFACTANT ANIONIC DETERGENT COMPOUNDS; B. ABOUT 5 TO 25 BY WEIGHT OF A PHOSPHATE-FREE WATER-SOLUBLE DETERGENCE ADJUSTING SALT; C. AN EFFECTIVE QUANTITY OF AN ENZYME OR A MIXTURE OF ENZYMES CHOSEN BETWEEN PROTEASE AND ALPHA-AMYLASES ALKALINES; D. AN ENZYME STABILIZATION SYSTEM CONTAINING, BASED ON THE WEIGHT OF THE DETERGENT COMPOSITION, ABOUT 12 TO 25 OF PROPYLENE-GLYCOL AND ABOUT II 1 TO 5 OF A BORON COMPOUND CHOSEN FROM BORIC ACID, L ' BORIC OXIDE AND BORATES OF ALKALINE METALS; AND E APPROXIMATELY 25 TO 75 BY WEIGHT OF WATER.

Description

The present invention relates to liquid detergent compositions

  stable compounds containing one or more enzymes-and a detergency builder, suitable for

  leaching or pre-soaking formulations more particularly

  In particular, the invention relates to compositions

  aqueous liquid solutions containing enzymes which

  hold a non-phosphated detergency builder and which are characterized as single-phase, clear, physically homogeneous liquid compositions

stable.

  The formulation of liquid detergent compositions

  Stabilized enzyme-containing compounds have been of particular interest in the prior art. The desire to incorporate enzymes into detergent compositions

  is mainly due to the efficiency of proteolytic enzymes

  lytic and amylolytic agents to break down

  tetinic and amylaceous found on soiled fabrics,

  in order to facilitate the removal of stains, for example

  full of sauce stains, blood stains, stains

  chocolate, etc., during the laundry operation

  during, the enzymatic materials suitable for

  laundering procedures, in particular proteolytic enzymes,

  are relatively expensive.

  generally the most expensive ingredient in a

  commercial liquid detergent composition, even when

  are present in relatively minor amounts

  In addition, enzymes are known to be unstable in

  This is the reason why the

  Liquid detergent swarms usually require a

  excess enzyme to compensate for the expected loss of

  enzymatic activity during prolonged periods of storage

  As a result, the prior art abounds in

  to stabilize the detergent compositions

  which contain enzymes, and in particular

  liquid positions without detergency builder by using

  various substances that are incorporated into the

  compositions and acting as enzyme stabilizers.

  In the case of liquid detergent compositions

  containing a detergency adjuvant, the problem of

  the enzyme is particularly acute.

  this is because detergency builders have a destabilizing effect on enzymes, even in compositions containing enzyme stabilizers which

  Moreover, they are effective in formulations without ad-

  In addition, the incorporation of an adjuvant

  detergency in a liquid detergent composition.

  another problem, namely the ability to form a stable solution with a single phase, the solubility of the

  sodium tripolyphosphate, for example, being relatively

  limited in aqueous compositions, and in particular

  in the presence of anionic and non-ionic detergents

  For example, the United Kingdom patent application

  No. 1,079,305 of January 20, 1982, describes a composition

  liquid detergent solution, with a detergency adjuvant

  The compositions described in the examples, however, instead of being stable, clear, single-phase solutions, are turbid suspensions which is stabilized by a mixture of a polyol and boric acid. who are likely to manifest

  separation after prolonged periods of storage.

  Therefore, the problems of enzyme stability

  my and the physical stability of the product are still

  problems to be overcome in formulating a com-

  liquid detergent position with detergency builder,

  containing enzymes, acceptable from the commercial point of view

cial.

  The present invention provides a stabilized, aqueous liquid detergent composition with adjuvant

  detergency, clear, single-phase, containing

  zymes, comprising: (a) about 8 to 20% by weight of one or more anionic surfactant detergents, (b) about 5 to 25% by weight of a water soluble, non-phosphated detergency builder salt; (c) an effective amount of an enzyme or enzyme mixture selected from the group consisting of proteases and alkaline alpha-amylases;

  (d) an enzyme stabilization system

  keeping, on the basis of the detergent composition, (i)

  12 to 25% of propylene glycol and (ii) about 1 to about% of a boron compound selected from the group consisting of boric acid, boric oxide and alkali metal borates; and

  (e) about 25 to 75% by weight of water.

  According to the process of the invention, the leaching of the stained and / or soiled materials is carried out by bringing these materials into contact with an aqueous solution of

  the liquid detergent composition defined above

  With respect to the enzyme-containing adjuvanted detergent compositions known in the art, the compositions of the present invention are

  whose characteristic is to be transparent, homogeneous and

  single-phase, and physically stable during

  extended periods of storage and in a wide range of

  temperature range In order to avoid the separation of

  of the invention, the compositions of the invention are preferably substantially free of the detergency builder salt of the

phosphate type.

  Unlike anionic detergent compositions

  With the presence of a detergency builder salt, the anionic surfactant contained in the compositions of the invention is solubilized in the presence of a detergency builder salt. In addition, the enzymatic compositions of the invention are characterized by the presence of an enzyme stabilization system which, in addition to providing long-term stability to the enzyme over a wide range of temperatures, serves to

  improve the solubility of the anionic surfactant and the ad-

  phosphate-free detergency of the aqueous composition, allowing the formation of a solution at a

  single phase, physically stable in the particular range

compositions indicated.

  The enzyme stabilization system according to the invention is a mixture of propylene glycol and a boron compound selected from boric acid, boron oxide and an alkali metal borate capable of reacting with propylene glycol The amount of propylene glycol ranges from about 12 to 25%, preferably from about 15 to 20%, by weight, and the amount of the boron compound may range from about 1 to 5%, preferably from about 1 to about 5%.

3%, by weight of the composition.

  Suitable alkaline proteolytic enzymes

  for the compositions of the invention comprise the di-

  liquid enzymatic preparations from the trade in

  intended for use in detergent compositions, powdery enzyme preparations being also useful to use, although, as a general rule,

  they are less convenient to incorporate into the

  liquid detergent with detergency builder.

  Thus, suitable liquid enzymatic preparations include "Alcalase" and "Esperase" sold by Novo

  Industries, Copenhagen, Denmark, and "Maxatase" and "AZ-

  Protease "sold by Gist-Brocades, Delft, The Netherlands.

  Esperase is particularly preferred for the composition of

  of the invention because of its optimized activity

  at the higher P H corresponding to the detergent compositions

with detergency adjuvant.

  Suitable liquid enzymatic preparations containing α-amylase include those sold by Novo Industries and GistBrocades under the trade marks of

  manufactures "Termamyl" and "Maxamyl", respectively.

  The synthetic anionic detergent used in

  the implementation of the invention can be any

  which of a great variety of such compounds well known and described in detail in Surface Active Agents, Vol II,

  by Schwartz, Perry and Berch, published in 1958 by Inters-

  Publishers, descriptions related to

  this detergent being incorporated by reference herein.

  The anionic detergent compounds which are

  in particular are (C 10-18 alkyl or C 20) benzenesulfonates in which the alkyl group comprises

  preferably 10 to 15 carbon atoms, the preference

  to a straight-chain alkyl radical of 12 or 13 atoms

  Preferably, such alkylbenzene sulphonyl

  has a high content of isomers in which the phenyl group is attached at the 3-position or higher and a corresponding low level (generally well below 50%) of isomers of which the phenyl group is attached in the 2-position or lower; in other words, the benzene ring is preferably attached largely to the 3, 4, 5, 6 or 7 position of the alkyl group and the content of isomers in which the benzene ring is attached to the position

  1 or 2 is weak in correspondence Examples of

  Surfactants of the alkylbenzene sulfonate type are described in U.S. Patent No. 3,320,174. Of course, alkylbenzene sulfonates can also be used.

  more strongly branched, but in general they are not

  not because of their lack of biodegradability.

  Other useful anionic detergents are olefin-sulfonates. In general, these contain

  long-chain alkenylsulfonates or hydroxyalkanes

  long chain sulfonates (the OH group being on

  the carbon atom that is not directly connected to the

  carbon number bearing the group -503 H) olefin-sulphate

  detergent fonate usually comprises a mixture of these types of compounds in varying amounts, often

  with long-chain disulfonates or sulphate-sulphonates

  These olefin sulfonates are described in patents such as U.S. Patents Nos. 2,061,618 and 3,409,637;

  N 3332880; N, 3,420,875; N, 3,428,654; N 3,506,580;

  and British Patent No. 1,129,158 The number of atoms

  carbon of the olefin-sulfonate is usually

  between 10 and 25, most commonly between 10 and 18 or 20, for example a mixture of mainly C 12, C 14 and C 16, having an average of about 14 carbon atoms, or a mixture mainly of C 14, C 16 and C 18 having

  an average of about 16 carbon atoms.

  Another class of useful anionic detergents is that of (higher paraffin) sulfonates. These can be primary paraffin sulfonates obtained by reacting long-chain alpha-olefins or bisulfites, for example sodium bisulfite, or paraffinsulfonates. whose sulphonate groups are distributed along the paraffinic chain, for example the products obtained by reacting a paraffin with

  long chaine with sulfur dioxide and oxy-

  gene under ultraviolet light, then neutralizing with sodium hydroxide or other suitable base (as in U.S. Patents 2,503,280; N 507,088;

  3,260,741; 3,372,188; and German Patent 735,096).

  Paraffin sulfonates preferably contain 13

  at 17 carbon atoms and this is normally the mono-

  sulfonate, but if desired, it may be di or trisulfonates, or higher sulfonates For example, the di and polysulfonates are used in mixture with a corresponding monosulfonate, for example, in the form of a mixture of mono and The hydrocarbon substituent thereof is preferably linear, but if desired, branched-chain paraffin sulfonates may be used, although they are less desirable from the point of view of the invention. biodegradability. Other suitable anionic detergents are sulphated ethoxylated higher fatty alcohols of formula RO (C 2 H 40) m 503 M, where R is a fatty alkyl group of 10 to 18 or 20 carbon atoms, m is between 2 and 6 or 8 (and preferably has a value of about 1/5 to 1/2

  number of carbon atoms of R) and M is a strong cation

  a solubilizing salt such as a metal cation

  calin, ammonium, lower alkylamino or lower alkanolamino, or a (higher alkyl) benzene sulfonate in

  which the alkyl group has from 10 to 15 carbon atoms

bone.

  Ethylene oxide is the lower alkylene oxide

  preferred for the alkoxy-type detergent

  anionic acid, and its proportion in the higher alkanol

  polyethoxylated sulfate is preferably from 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, three moles constituting the amount which is

  prefers, especially when the higher alkan 6

  In the case of maintaining the desired hydrophilic-lipophilic ratio, when the carbon atom content of the alkyl chain is within

  the lower part of the range from 10 to 18 carbon atoms

  bone, the ethylene oxide content of the detergent can e-

  be reduced to about two moles per mole, while

  that the higher alkanol has 16 to 18 carbon atoms

  bone and is in the upper part of the range, the number of ethylene oxide groups can be increased to 4 or 5 and in some cases up to 8 or 9 so

  similar, the salt-forming cation may be modified

  It can be any suitable solubilizing metal or radical, but it is most often an alkali metal, for example

  of sodium, or ammonium.

  kylamine or lower alkanolamine, alkyl groups

  and alkanols generally comprise 1 to 4 carbon atoms.

  bone, and amines and alkanolamines can be

  mono-, di and trisubstituted, for example monoethanol

  lamin, diisopropanolamine and trimethylamine.

  Poly- (lower alkoxy) (higher alkanol) sul-

  can be used in combination with other

  very preferred anionic detergents such as

  higher) benzenesulfonates to confer the de-

  The preferred polyethoxylated alcohol-sulfate detergent is available from the Shell Chemical Company and is available from the detergent adjuvant liquid detergent compositions of this invention.

  is marketed under the designation "Neodol 25-35".

  Examples of polyethenoxy (higher alcohol)

  O sulfates that can be used in compositions

  liquid detergents of the invention include the following

  : (mixed normal or primary C 12 15 mixed alkyl)

  sodium thenoxysulphate; myristyl sulfate triéthénoxy

  potassium; dietetic n-decyl-diethenoxysulfate

  mine; ammonium lauryl diethenoxy sulphate; palmityl-

  sodium tetraethenoxy sulphate; (normal mixed alkyl)

  or primary C 14-15) (tri and mixed tetra-ethenoxy)

  sodium fate; stearyl pentaethenoxy sulfate

  methylamine; and (normal or primary mixed alkyl

  Clo 18) potassium triethenoxy sulfate.

  Other useful anionic detergents include

  the (higher acyl) sarcosinates, for example N-lau-

  sodium royl-sarcosinate; (higher fatty alcohol)

  sulphates such as sodium lauryl sulphate and (al-

  cool of tallow) sodium sulfate; sulphated oils;

  sulfates of mono or diglycerides of higher fatty

  such as monoglyceride monoglyceride

  America; although of these, it has been found that sodium (higher alcohol) sulphates are lower than polyethoxylated sulphates in the detergency of aromatic poly (alkenoxy) -ether-sulphates

  such as sulphates of oxy-

  of ethylene and nonylphenol (generally having 1 to 2 oxyethylene groups per molecule, preferably 2 to

  12); polyethoxy (higher alcohol) sulphates and alcohols

  kylphenol-polyethoxy-sulphates having an alcoholic substituent

  lower xy (1 to 4 carbon atoms, for example

  thoxy) on a neighboring carbon atom

  sulfate group, for example monomethyl monoethane

  monosulphate of a long-chain vicinal glycol, for example a mixture of vicinal alkanediols of 16 to 20 carbon atoms of straight chain; acyl esters of

  isethionic acid, for example the isethionates of o-

  Leyle; acyl-N-methyl-taurides, for example the N-methyl

  thyl-lauroyl or potassium oleyl-taurides; Sal-

  higher alkyl) phenyl-polyethoxy-sulfonates; The (alky-

  the higher) phenyl-disulfonates, for example pentadec

  cyl-phenyl-disulfonate; and higher fatty acid soaps

  such as mixed coconut oil soaps

and tallow at a ratio of 1: 4.

  Of the above types of anionic detergents

  sulphates and sulphonates are generally

  but the organic phosphates and phosphonates cor-

  Respondents may also be used when their phosphorus content is not harmful. In general,

  synthetic organic anionic detergents hydrosolu-

  (including soaps) are salts of alkali metal cations, for example potassium, lithium, and in particular sodium, although ammonium cation salts

  and substituted ammonium cations, for example those

  described, for example triethanolamine, triisopropyl

  pylamine, can also be used.

  It may be possible to resort to a

  nonionic gent in minor amounts to enhance the anionic detergent compound of the present compositions

  liquid detergents with a detergency builder

  that it is used in this combination with a detergent

  anionic, the amount of nonionic detergent is generally

  less than about 10%, and preferably

  less than about 5% by weight, relative to the composition of

total.

  Nonionic detergents are generally polyalkoxylated lipophilic compounds in which the

  desired hydrophilic-lipophilic ratio is obtained by ad-

  Addition of a hydrophilic poly (lower alkoxy) group to a lipophilic unit In the case of compositions according to the invention,

  the nonionic detergent used is preferably

  a lower poly (lower alkoxy) alkanol in the

  which alkanol group has 10 to 18 carbon atoms

  and wherein the number of moles of alkylene oxide

  lower (2 or 3 carbon atoms) is between 3 and 12 Of these materials, it is preferred to use those in

  which the higher alkanol is a higher fatty alcohol than

  11 or 15 to 15 carbon atoms and which contains

  5 to 8 or 5 to 9 lower alkoxy groups per mole. The lower alkoxy is preferably the ethoxy group, but in some cases it may be in admixture with a propoxy group, this group, if present, being generally a minor constituent (less than 50%) Examples of such compounds are those in which the alkanol group

  contains 12 to 15 carbon atoms and contains

  about 7 ethylene oxide groups per mole, for example

  Neodol 25-7 and Neodol 23-6.5, these products being

  Shell Chemical Company, Inc. The first is a

  condensation product of a mixture of higher fatty alcohols

  on average about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide, and the last is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups per mole is on average about 6.5 The higher alcohols are primary alkanols Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, both

  being ethoxylates of linear secondary alcohols

  bricks by Union Carbide Corporation The first is a

  mixed ethoxylation product of a secondary alkanol

  from 11 to 15 carbon atoms with seven moles of oxy-

  ethylene, and the latter is a similar product but

  having nine moles of reacted ethylene oxide.

  Also of interest in the compositions of the present invention are higher molecular weight nonionic compounds, for example Neodol 45-11 which

  are analogous condensation products of ethylene oxide

  and higher fatty alcohols, the higher fatty alcohol having 14 or 15 carbon atoms and the number of groups

  ethylene oxide per mole being about 11

  Duits are also manufactured by Shell Chemical Company.

  Other useful nonionic detergents are Plurafac B26 (BASF Chemical Company), the product of

  the reaction of a higher linear alcohol and a mixture of

  ethylene oxide and propylene oxide.

  In the lower poly (lower alkoxy) alkanols

  the best ratio of hydrophilic and

  pophiles is obtained when the number of alkoxy-

* lower is equal to about 40% to 100% of the number of ato-

  carbon monoxide and higher alcohol, preferably 40 to 60% of this number The nonionic detergent is constituted

  preferably at least 50% of the ethoxylated alkanols

  Alkanols of higher molecular weight and di-

  to other nonionic detergent compounds normally

  solids and surfactants can contribute to the gelation

  liquid detergent composition and, consequently,

  they are normally avoided or used only in limited amounts in the compositions of the invention, although minor proportions may be used because of their cleaning properties, etc. As far as non-detergents are concerned, Preferred ionic and less preferred ionic groups, the alkyl groups present are preferably linear, although a certain degree of branching can be accepted, for example on the atom following the terminal carbon atom of the straight chain or with two atoms.

  of this terminal atom and away from the

  thoxylated provided that this branched alkyl group has a

  chain length not exceeding three carbon atoms

  Normally, the proportion of carbon atoms

  in such a branched configuration is minor, and

  rarely exceed 20% of the total carbon atom content

  alikyl group bone Similarly, although the

  linear Te groups which are connected by their

  mitted to ethylene oxide chains are highly

  preferable and be considered as ensuring the combination

  optimum characteristics of detergency, biodegradability and non-gelling properties, it can be

  produce a median or secondary bond to the oxide of

  thylene in the chain In this case, it usually wears

  only a small proportion of these alkyl groups, generally less than 20%, but in the case, for example, of the above-mentioned Tergitols, this proportion

  can be superior also when the oxy-chain

  of lower alkylene contains propylene oxide,

  this is usually less than 20%, and pre-

  less than 10% of said chain.

  Adjuvant salts of phosphate-free detergents

  are used in the compositions of the present invention.

  in proportions between about 5 and 25%,

  and preferably from about 10 to 20% by weight.

  peculiarities of mineral detergency additives

  soluble substances without phosphorus include carbonates,

  bicarbonates and hydrosoluble mineral silicates

  in particular here alkali metal carbonates, bicarbonates and silicates, for example sodium and

of potassium.

  The water-soluble organic adjuvants are also

  are useful and include polyacetates, carboxylates,

  alkali metal polycarboxylates and polyhydroxysulphonates

  Ammonium and substituted ammonium.

  of polyacetates and polycarboxylates used co M-

  detergency builders include sodium salts,

  potassium, lithium, ammonium and substituted ammonium of the

  ethylene diaminetetraacetic acid, nitriloacetic acid

  triacetic acid, benzene-polycarboxylic acids (that is,

  ie, penta and tetra-), carboxymethoxys-

cinique and citric acid.

  The proportions of water, the main solvent of the compositions of the present invention, are generally from about 25 to 75%, preferably from 40% to 60% by weight.

  relative to the weight of the liquid composition.

  Fluorescent optical brightening agents used

  in liquid detergent compositions are

  important components of the detergent compositions

  tiles that give a shiny look to laundry and washed materials, so that laundry is not only

  clean, but also gives an impression of cleanliness.

  Although it is possible to use a single

  for a particular purpose in composi-

  liquid detergent formulations of the invention, it is generally

  It is desirable to use brightening agent mixtures which exert satisfactory brightening effects on cotton.

  "Nylons", polyesters and mixtures of these

  which are also stable with respect to the agent

  bleaching A suitable description of these types

  Optical brightening agents can be found in the article "The Requirements of Present Day Detergent Fluorescent Whitening

  Agents of A Siegrist, JA Oil Chemists Co., Jan.

  1978 (volume 55) This article and the U S patent

  3 812 041 of 21 May 1974 which are quoted as references

  contained detailed descriptions of a large number of

  diversity of suitable optical brighteners.

  Among the brightening agents useful in

  liquid detergent formulations of the present invention,

  may mention: Calcofluor 5 BM (American Cyanamid); calc

  fluorine White ALF (American Cyanamid); SOFA-2001 (Ciba);

  CDW (Hilton-Davis); Phorwite RKH, Phorwite BBH and Phor-

  wite BHC (Verona); CSL, powder, acid (American Cyanamid);

  FB 766 (Verona); Blancophor PD (GAF); UNPA (Geigy); Ti

nopal RBS 200 (Geigy).

  Liquid detergent compositions may contain adjuvants intended to impart properties

  additional, functional or aesthetic

  useful agents include suspending agents, or anti-redeposition agents, for example polyvinyl alcohol.

  that sodium carboxymethylcellulose, hydroxypropyl-

  methyl-cellulose; thickeners, for example gums, alginates, agar; foam boosters, for example lauric-myristic diethanolamide; foam destroyers, for example silicones; bactericides, for example tribromosalicylanilide,

  hexachlorophene; dyes; pigments (

  sands in water); conservatives; ultraviolet light absorbers; fabric softeners;

  opacifiers, for example suspensions of polystyrene

  rein; and fragrances Naturally, these materials will be

  chosen on the basis of the properties desired for the

  completed, of their compatibility with the other

  and their solubility in the free composition.

quide.

  The liquid compositions of the invention are

  effective and easy to use.

  For example, using a typical preferred formulation of the present invention, the use of much smaller volumes of the liquids of the invention is required to obtain a comparable cleaning of the laundry. about 132 g or

  half a cup of liquid for a tank full of

  automatic washing machine with top loading in which the volume of water is 55 to 75 liters; and even less is needed for load-loading machines

  the front Thus, the concentration of the composition de-

  liquid sediment in the wash water is of the order of

  In general, the proportion of free composition

  the solution in the washing solution is between

  0.05 and 0.3%, preferably between 0.15 and 0.25%.

  The proportions of the various constituents of the composition

  liquid may vary accordingly.

  Equivalent results can be obtained using larger proportions of a more dilute formulation, but the larger amount required will require

  packaging supplement and will generally be less

only for the user.

EXAMPLE 1

  Enzyme-adjuvanted and enzyme-containing liquid detergent compositions A-E are formulated as described in Table I. The percentages shown are

percentages by weight.

Table 1

Dodecylbenzene sulfonate -

Sodium

Alcohol sulfate-C 12 _ 15 etho-

  xylated (3 moles EO * / mole alcohol)) Brightening agent Sodium nitrilotriacetate

PBB (2)

  Perfume Enzyme Protease (3) Propylene Glycol Borax H 20 A B

7% 7%

C D E

7% 7% 7%

7 7 7 7

0.2 0.2 0.2 0.2

15 15 15

1 1 11

0.3 0.3 0.3 0.3

1 1 1 1

20 20

1 2

  --the remainder Percentage of enzyme activity after (a) 4 days at 43 ° C (b) 6 days at 43 ° C

__ 98%

61 86 88

  (1) Neodol 25-3 S sold by Shell Oil Company.

  (2) Polar Brilliant Blue (Polar Brilliant Blue) -

1% solution of active dye.

  0.2 0.3 (3) Esperase sold by Novo Industries containing 5%

  75% propylene glycol, the remainder

  both in H 20 with an activity of 8.0 KNPU / g (kilogram

  units of Novo Protease / g) (*) EO (ethylene oxide) The enzymatic activities of the AE compositions are tested after 6 days of storage at 43 ° C, the percentage of activity relative to the initial value being indicated on Table I Activity after 4 days is measured only for composition E

  compositions A and B are the only compositions

  not having a system that stabilizes the enzymes according to

  and they manifest a total loss (composi-

  A) or almost complete (composition B) of the enzymatic activity after 6 days. Compositions C, D and

  E reflect the marked improvement in the stability of

  zymes attributed to the incorporation of propylene glycol and

  borax in the detergent composition.

  Compositions B to E are all clear, single-phase homogeneous solutions which retain their physical stability and their clarity after 6 months of

  storage at room temperature and at 43 ° C.

  position A which does not conform to the invention is physically

  unstable because of the lack of propylene-gly-

  which, in addition to its role of stabilizing the enzymes (together with the above-mentioned boron compound), promotes

  the solubility of anionic detergents and NTA (nitrate

  lotriacetate) adjuvant in the aqueous composition.

EXAMPLE 2

  Liquid detergent compositions F and G with

  detergency adjuvant and containing enzymes are

  in a manner substantially analogous to the compositions A-E except that the adjuvant salt used is

  detergency sodium citrate instead of sodium NTA.

  The compositions are presented below in Table II.

Table II

  Sodium dodecylbenzene sulfonate Ethoxylated C 12 - 15 sulfate alcohol (3 moles EO / mole alcohol) Sodium citrate brightening agent

PBB (1)

  Perfume Enzyme protease (2) Propylene glycol Borax H 20 F 7% G 7%

7 7

0.2 0.2

12 12

1 1

0.3 0.3

1 1

20

  the rest Percentage of activity after 4 days to enzymatic 43 C

  (1) "Polar Brilliant Blue" a 1% color solution

active.

  (2) "Esperase" sold by Novo Industries containing 5% enzyme, 75% propylene glycol, the remainder being H20 having an activity of 8.0 KNPU / g (kilo-units)

Novo Protease / g).

  Composition B according to the invention exhibits a

  enzymatic activity after four days of 95%, com-

  parative to the composition F which does not contain any

  boron compound and therefore loses more than three

  quarter of its initial enzymatic activity.

  Both compositions are clear solutions

  single-phase that remain physically stable after six months of storage at room temperature and

at 43 C.

EXAMPLE 3

  Liquid detergent compositions H, I and J

  with an adjuvant and an enzyme are formulated

  essentially analogous to compositions F and G of

  Example 2 except that they contain a

  protease and alpha-amylase mixture instead of protease only The compositions are presented below in Table III.

Table III

  Sodium dodecylbenzene sulfonate Ethoxylated C 12 - 15 sulfate alcohol (3 moles EO / mole alcohol) Sodium citrate brightening agent

PBB (1)

  Perfume Enzyme protease (2) Enzyme a-amylase (3) Propylene glycol Borax H 20 Percent of enzymatic activity after 4 days at 43 C Enzyme-aamylase Enzyme Protease H 7% I 7% J 7 /

7 7 7

0.2 0.2 0.2

12 12 12

1 1 1

0.3 0.3 0.3

1 1 1

0.4 0.4 0.4

20 20

1 3

  the rest% 67% 87% (1) "Polar Brilliant Blue" a 1% solution of active dye (2) "Esperase" sold by Novo Industries containing 5%

  75% propylene glycol, the remainder

  both in H 20 with an activity of 8.0 KNPU / g (kilogram

units of Novo Protease / g).

  (3) "Termamyl" sold by Novo Industries containing 5% enzyme, 18% NaCl, the remainder consisting of H having an activity of 120,000 units of Novo amylase

per gram.

  Compositions I and J according to the invention are

  have a much more stable enzymatic activity after four days in the case of protease and

  amylase compared with the composition H which does not

  does not retain boron, and therefore loses about half of its initial amylolytic activity and about one third of its initial proteolytic activity during

the four-day period.

  The three compositions are clear solutions

  single-phase ones that remain physically stable

after six months of storage.

Claims (13)

R E V E N D I C A T IO N S   1 stabilized composition, aqueous, with adjuvant   clear, single-phase, liquid and containing one or more enzymes, characterized in that it comprises: (a) about 8 to 20% by weight of one or more surfactant anionic detergent compounds; (b) about 5 to 25% by weight of a water-soluble, non-phosphated detergency builder salt; (c) an effective amount of an enzyme or enzyme mixture selected from the group consisting of alkaline proteases and alpha-amylases;   (d) an enzyme stabilization system   keeping, on the basis of the weight of the detergent composition, (i) about 12 to 25% of propylene glycol and (ii) about   1 to 5% of a boron compound selected from the group   taking boric acid, boric oxide and alkali metal borates; and   - (e) about 25 to 75% by weight of water.   Detergent composition according to Claim 1, characterized in that the detergency builder salt is sodium citrate.   Detergent composition according to Claim 1, characterized in that the said adjuvant detergency salt   is sodium nitrilotriacetate.   4 Detergent composition according to claim 1, characterized in that it is substantially free   phosphate-type detergency builder.   Detergent composition according to Claim 1, characterized in that it contains approximately 15 to 20% by weight of propylene glycol and approximately 1 to 3% by weight said boron compound.   Detergent composition according to claim 1, characterized in that said boron compound is borax. Detergent composition according to Claim 1, characterized in that the said adjuvant detergency salt   is present in a proportion of about 10 to 20% by weight.   Detergent composition according to Claim 1, characterized in that the anionic detergent is a mixture of a C 10 -C 18 alkyl benzene sulphonate and a   polyethoxylated C 10 C 18 alcohol sulphate.   Washing process, characterized in that it consists in bringing the stained and / or soiled tissues into contact with a single-phase, clear, liquid detergent composition with adjuvant and containing one or more enzymes, comprising (a) ) about 8 to 20% by weight of one or more anionic detergent compounds   surfactants; (b) about 5 to 25% by weight of an ad-   phosphate-free and water-soluble detergent builder; (c) an effective amount of an enzyme or enzyme mixture selected from the group consisting of proteases   and alkaline alpha-amylases; (d) a stabilization system   of enzymes containing, on the basis of the weight of the   detergent composition, (i) about 12 to 25% of propylene   ne-glycol and (ii) about 1 to 5% of a boron compound selected from the group consisting of boric acid, oxide   boric acid and borates of alkali metals; and (e) 25 to 75% by weight of water.   Process according to claim 9, characterized   in that the adjuvant salt of detergency is sodium trate.   The process according to claim 9, characterized   in that the detergency builder salt is nitrilo sodium triacetate.   Process according to claim 9, characterized   in that the detergent composition is substantially   phosphate free detergent builder.   Method according to claim 9, characterized   in that the detergent composition contains about 15 to 20% by weight of propylene glycol and about 1 to 3% by weight of borax.   The method of claim 9, characterized   in that said detergent composition contains about 10 to 20% of a detergency builder salt of the type not phosphated.   The process according to claim 9, characterized   in that the detergent composition contains a   (C1-C18 alkyl) benzene sulfonate and a   polyethoxylated C 10 -C 18 cool sulfate.