FR2585361A1 - STABILIZED REINFORCED LIQUID DETERGENT COMPOSITION CONTAINING ENZYMES AND FABRIC SOFTENING, AND METHOD FOR ITS IMPLEMENTATION - Google Patents

Abstract

THE INVENTION RELATES TO A STABILIZED REINFORCED LIQUID DETERGENT COMPOSITION CONTAINING ENZYMES, AND SOFTENING LAUNDRY. THE SAID COMPOSITION CONTAINS DETERMINED PROPORTIONS OF SURFACE-ACTIVE DETERGENT COMPOUNDS, ADJUSTING SALTS OF DETERGENCE, BENTONITE, ENZYME OR MIXTURE OF ENZYMES, OF AN ENZYME STABILIZATION SYSTEM CONTAINING DETERMINED PROPORTIONS OF GLYCOSE, COMPOUNDS BORON AND CARBOXYLIC ACID COMPOUND, AS WELL AS WATER AND POSSIBLE OTHER MINOR ADDITIVES. APPLICATION TO LAUNDRY WASHING.

Description

The present invention relates to composi-

  enhanced, stable liquid detergent

  enzymes, suitable for

  washing or pre-washing the laundry. More specifically

  the invention relates to detergent compositions

  aqueous liquids containing enzymes which

  hold one or more detergency adjuvants and

  which are characterized in that they are composi-

  homogeneous liquid, physically stable

  The prior art has strongly

  concentrated on the formulation of compositions

  stabilized liquid gents containing enzymes. The desire to incorporate enzymes into detergent compositions is primarily based on the efficiency

  proteolytic and amylolytic enzymes to decom-

  ask the protein and amylaceous materials that are

  soiled fabrics, which facilitates the elimination of

  stains, eg sauce stains, blood stains, chocolate stains, etc.,

  during the laundry. However, the subjects

  zymes suitable for whitening compositions

  cheating, in particular proteolytic enzymes,

  are relatively expensive. In fact, they are

  mi the most expensive ingredients of a composition

  commercial liquid detergent, even though

  are present in relatively small amounts

  res. In addition, enzymes are known to be

  tables in aqueous compositions. That's the reason

  for which it is generally necessary to use

  excess of enzymes in detergent formulations

  liquids to compensate for the expected loss of enzymatic activity during prolonged periods of storage. Therefore, the prior art abounds in proposals for stabilizing compositions

  liquid detergents containing enzymes, and in particular

  particularly unreinforced liquid compositions, using various materials which are incorporated in the composition to act as enzyme stabilizers. In the case of detergent compositions

  liquids containing a detergency builder, the

  the instability of enzymes is particularly

  acute. This is mainly due to the fact that

  detergency additives exert a destabilizing effect

  enzymes, even in

  enzyme stabilizers, which are

  their effective in unreinforced formulations.

  In addition, the incorporation of a detergency builder into a liquid detergent composition poses another problem.

  problem, namely that of being able to form a

  stable phase in one phase; the solubility of the

  sodium tripolyphosphate, for example, being

  limited in aqueous compositions, and in particular in the presence of anionic detergents

and nonionic.

  In British Patent Application N

  2 079 305, a liquid detergent composition is described.

  of enhanced aqueous containing enzymes, which is

  stabilized by a mixture of a polyol and boric acid

  than. As mentioned in the examples of this application,

  of, relatively large amounts of glycerol

  are needed to stabilize the enzymes of the com-

  position. However, as highlighted in the following

  this memoir, the stabilizing effect of

  zymes provided by a mixture of glycerin and borax

  in an aqueous liquid detergent composition which strengthens

This is relatively moderate.

  In the published European patent application

  0 126 505, a composition is described which

  aqueous liquid containing enzymes and

  an enzyme stabilizing mixture consisting of certain dicarboxylic acids and borax. Dicarboxylic acids are recommended as a substitute for a polyol such as glycerol in

  known mixtures of enzymes stabilization con-

  with glycerol and a boron compound. How-

  dant, the dicarboxylic acid-borax mixtures of

  this publication, as well as the glycerol mixture

  The above-mentioned prior art and borax provide at most a moderate stabilizing effect in liquid-enhanced detergent compositions.

the present invention.

  The present invention provides a composition

  strengthened, stabilized liquid detergent

  containing enzymes, comprising: (a) about 5 to 20% by weight of one or more surfactant detergent compounds selected from

  anionic, nonionic and ampho-

  teria; (b) about 5 to 30% by weight of one or more

  adjuvant detergency salts selected from

  polyphosphates of alkali metals, carbonates of

  alkali metals, nitrilotriacetates of

  hollies and polyacetal carboxylates;

  (c) about 5 to 20% by weight of a swelling clay

  flante of the bentonite type; (d) an effective amount of an enzyme or

  enzyme mixture selected from alkaline enzymes

  protease and alpha-amylase type;

  (e) an enzyme stabilization system containing

  on the basis of the weight of the detergent composition

  (i) about 1 to 10% glycerin; (ii) approximately

  1 to 8% of a boron compound selected from boiling acid

  boric oxide and alkali metal borates

  and (iii) about 0.5 to 8% of a compound of the type

  carboxylic acid selected from mono-, di-

  and / or polycarboxylic of 1 to 8 carbon atoms and their water-soluble salts; and (f) the remainder consisting of water and possibly

in perfume and other additives.

  In a preferred embodiment of

  the invention, the liquid detergent composition comprises

take: -

  (a) about 5 to 15% of an alkylbenzene sulfonate

  alkali metal salt in which the alkyl group

  holds from 12 to 15 carbon atoms;

  (b) about 2 to 5% of an alkylpolyethoxy sulfa

  alkali metal salt in which the alkyl group

  holds from 10 to 18 carbon atoms and the poly-

  ethoxy has from 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from about 2: 1 to about 6: 1;

  (c) about 5 to 20% of sodium tripolyphosphate

  dium; (d) about 1 to 10% of sodium carbonate, sodium bicarbonate or a mixture thereof, the weight ratio of (c) to (d) being from about 2: 1 to about 6: 1; (e) about 10 to 15% sodium bentonite;

  (f) an effective amount of the enzyme or metabolism

enzyme mixture mentioned above;

  (g) an enzyme stabilization system

  on the basis of the weight of the composition

  (i) about 1 to 5% glycerin, (ii) about 1 to 5% of an alkali metal borate, and (iii) about 0.5 to 4% of said carboxylic acid compound; and

  (h) the remainder consisting of water and, optionally

in perfume and other additives.

  According to the method of the invention, the washing of stained and / or soiled materials is carried out by bringing these materials into contact with a solution

  aqueous detergent compositions defined

above.

  The liquid detergent described is a deter-

  for heavy laundering work,

  ceptable for commercial purposes, able to clean

  suitably laundry with both

  oily and particulate cracks. In addition, the compositions described can be used for the pretreatment of very dirty parts, such as necks

  and wrists, articles to wash.

  The present invention is based on the discovery of a three-component enzyme stabilization system as defined herein, which provides an enzyme stabilizing effect to the liquid detergent compositions of the invention much greater than

  the one that can be obtained with stabilizers from

  classic zymes. The stabilizing effect of the enzymes thus obtained is the result of a synergy of the three

  components. According to the invention, the stability of the enzymes

  provided by a mixture of glycerin and borax or a mixture of borax and a dicarboxylic acid, as described in the prior art, can be improved synergistically using the system.

  three-component stabilizer defined herein in

  liquid positions of the invention, so as to raise

  the degree of stability of the enzymes far above that

  supplied either by the mixture of glycerine and

  the mixture of borax and dicarboxylic acid

  when used independently of one another as enzyme stabilizers. For purposes

  commercial enzymes, a desirable enzyme stability

  generally corresponds to about one half-life of a se-

maine at a temperature of 43 C.

  The enzyme stabilization system

  of the invention is a mixture of glycerin, a

  boron selected from boric acid,

  and an alkali metal borate and a carboxylic acid compound as defined herein. The weight of the stabilizing system contained in the compositions

  reinforced liquid detergents of the invention

  In general, it is found that about 6 to 15% of the weight of these compositions is from about 3 to about 25% by weight. The weight ratio of glycerin to borax of the stabilizing mixtures is generally from about 0.5 to 3. The preferred amount of glycerin in the composition is from about 1 to 1%, the preferred amount of the boron compound is

  about 1 to 5%, and the preferred amount of

  The carboxylic acid content is about 0.5 to 4%, based on

the weight of the composition.

  The carboxylic acid compounds which are useful in the enzyme stabilization system of the invention include saturated as well as unsaturated monocarboxylic acid polycarboxylic acids having 1 to 8 carbon atoms, of which

  mention may be made of oxalic acid (HOOCCOOH), malic acid

  (HOOCCH2COOH), maleic acid (HOOCCH: CHCOOH) and succinic acid (HOOCCH2CH2COOH). Acids

  carboxylic acids may contain hyphenated substituents

  droxy or amino, such as malic acid

  (HOOCCHOHCH2COOH), tartaric acid (dihydro-

  xysuccinic), aspartic acid (amino-succinic acid)

  nique) and citric acid. Preferred carboxylic acids of the invention are aspartic acid,

  tartaric acid, malonic acid and maleic acid

  lic. From a commercial point of view, a carboxylic acid

  Particularly preferred is citric acid and / or its salts because of their relatively low price.

  The alkaline proteolytic enzymes con-

  coming from the compositions of the present invention

  take the various enzymatic preparations

  trade partners having been developed to be

  used in detergent compositions. The pre-

  enzymatic partes in the form of powder are also

  useful although, as a general rule, they

  less convenient to incorporate into the composi-

  enhanced liquid detergent solutions. Thus,

  appropriate liquid enzymatic preparations

  take "Alcalase" and "Esperase", sold by Novo Industries, Copenhagen, Denmark, and "Maxatase" and

  "AZ-Protease" sold by Gist-Brocades, Delft, Netherlands

Low.

  Among the enzyme preparations

  appropriate types of the α-amylase type, it may be

  those sold by Novo Industries and Gist-Bro-

  under the trademarks "Termamyl" and

"Maxamyl", respectively.

  "Esperase" is particularly preferred for the compositions of the invention, because of

  its optimized activity at higher pH values

  res corresponding to the detergent compositions

  forced. The preferred detergents intended to be

  used in the liquid compositions of the invention

  are the synthetic anionic detergent compounds

  ticks, and in particular a mixture of (higher alkyl)

  benzene sulphonate and alkylpolyethoxy sulphonate

  you. Although the formulas of the present invention may also contain other water-soluble (higher alkyl) benzene sulfonates, e.g.

  potassium and, in some cases, ammonium salts

  nium or alkanolammonium, where appropriate, it has been found that the sodium salt is the one

  prefers, which is also the case with regard to

  does the detergent component alkyl-polyethoxy-sulfate.

  The alkylbenzene sulfonate is the one in which the higher alkyl group contains from 12 to 15 carbon atoms.

  carbon, preferably 13 carbon atoms, alkyl

  polyethoxy sulfate, which may also be referred to as sulfated polyethoxylated higher linear alcohol or the sulfated condensation product of a fatty alcohol

  and ethylene oxide or polyethoxylene-

  glycol, is the one in which the alkyl group

  10 to 18 carbon atoms, preferably 12 to 15 carbon atoms, for example about 13 carbon atoms, and which contains from 3 to 11 ethylene oxide groups, preferably from 3 to 7, more preferably from 3 to 5, and in particular 3 or about 3 ethylene oxide groups. The ratio of alkyl benzene sulfonate to polyethoxy sulfate in the detergent mixture is preferably from about 2: 1 to 6: 1, and more preferably

  from about 2: 1 to 4: 1 by weight. At higher ratios

  at 5: 1, the physical stability of the product may

to be badly affected.

  In appropriate cases, other deter-

  anionic agents such as fatty alcohol sulfates, paraffinsulfonates, olefin sulfonates,

  monoglyceride sulphates, sarcosinates and deter-

  similar function, preferably in the form of

  Alkali metal salts, for example sodium, may be present, sometimes as a partial replacement for the synthetic organic detergents mentioned above, but in general their possible presence is added to that of such detergents. Normally, the additional detergents are sulphated products

  or sulphonated (usually in the form of

  dium) and contain fatty or linear alkyl groups.

  long chain areas (8 to 20 carbon atoms). In

  more of all synthetic organic anion detergents

  In addition, nonionic and amphoteric materials may also be present, such as Neodol (R), sold by Shell Chemical Company, which are ethylene oxide and higher fatty alcohol condensation products, for example Neodol ( R) 23-6.5,

  which is a condensation product of a fatty alcohol

  of about 12 or 13 carbon atoms with about

  6.5 moles of ethylene oxide. Examples of

  detergents and various classes of detergents

  can be found in Surface Active Agents, Vol. II, Schwartz, Perry and Berch (Interscience

Publishers, 1958).

  The combination of adjuvant salts of deter-

  of the present invention, which has proved to be

  suitable for improving the detergency of the

  of synthetic anionic organic detergents and produce the desired pH in the liquid detergent and

  in wash water, is a mixture of tripolyphos-

  podium of sodium and sodium carbonate. Salts

  detergency builders are used in the compo-

  of the present invention in proportions

  generally from about 5 to 25% by weight. In the com

  In the preferred combination of detergency builder salts, sodium tripolyphosphate is present in amounts of about 5 to 20%, preferably 10 to 16%, and the sodium carbonate is present in about 1 to 10% by weight. preferably 3 to 7%, the ratio in

  weight of carbonate tripolyphosphate in

  Preferred detergency adjuvants are from about 2: 1 to about 6: 1, and more preferably from about 2: 1 to about 4: 1. As used herein, the terms "carbonates" or "carbonate" of alkali metal refer to the carbonates,

  bicarbonates and sesquicarbonates of such alkali metals

lins.

  To achieve the best properties of

  easier mixing and use.

  satisfactory final concentration, it is preferable that sodium tripolyphosphate be of low

  Phase I type tripolyphosphate.

  Phase I type tripolyphosphate content is less than 30% of the tripolyphosphate used. Well

  that in some cases tripolytic

  Incompletely neutralized phosphate, the phosphate that is used can normally be considered

  being pentasodium tripolyphosphate Na5P3010. evident

  in some cases, for example in the presence of

  potassium salts or other materials, the exchange of

  ion in an aqueous medium may give salts other than sodium tripolyphosphate, but

  For the purposes of this specification, it is considered that

  sodium polyphosphate, in the form of the pentasodium salt

  that, which is the material normally introduced into the mixer to make the liquid detergent of

  the invention is the tripolyphosphate used.

  Other adjuvant salts detergents pre-

  which can be used instead of tripoly-

  Sodium phosphate and sodium carbonate, or in addition thereto, include a polyacetal carboxylate as described herein and sodium nitrilotriacetate (NTA). Obviously, we can use various mixtures

  water-soluble adjuvant detergent salts

  born. However, the tripolyphosphate-carbonate mixture described has been most advantageous, although other detergency builders and mixtures thereof are also useful. Other detergency builders that can be used as supplements, in addition to

  proportions of the above-mentioned detergency builders

  born, include other phosphates such as pyro-

  tetrasodium phosphate or tetrapotassium pyrophosphate

  sodium bicarbonate, sodium citrate, glutamate

  sodium carbonate, sodium silicate, and sesqui-

  sodium carbonate. Among the water-insoluble detergency builders that can be used are

  zeolites, such as Zeolite A, generally

* in the form of its crystalline hydrate, well

  that amorphous zeolites can also be used

the.

  Polyacetal carboxylates are generally

  described in U.S. Patent Nos. 4,144,226.

  and U.S. Patent No. 4,315,092. U.S. Patent 4,146,495 discloses

  written detergent compositions containing poly-

  acetal carboxylates as detergency builders.

  The polyacetal carboxylates which are used

  here as detergency builders may be

  as described in U.S. Patent No. 4,144,226 and may be prepared by the process referred to therein. An example of such a product is represented by the formula: R1 - (C0O) n -R2 n! COOM o M is selected from an alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms,

  tetraalkylammonium groups and alkanolamines

  ne, these last two groups having 1 to 4 carbon atoms in their alkyl portions, n is equal on average to at least 4, and R1 and R2 are chemically stable groups that stabilize the polymer to

  against rapid depolymerizations in solution

  cuddly. Preferably, the polyacetal carboxylate is that in which M is an alkali metal, for example sodium, n is from 50 to 200, R is MOOC.

CH3CH2?

HCO- or H3C-CO-

  h-C MOOC or a mixture of these groups, R2 is

OCH2CH3

  -CH! CH3. and has an average value of 20 to 100, preferably 30 to 80. The calculated weight average molecular weights of the polymers are normally in the range of 2000 to 20000, preferably 3500 to 10000, and more preferably 5000. at 9000, for example

about 8000.

  Sodium polyacetal carboxylate,

  most preferred is sold by Monsanto Company and

  is known as Builder U. It has a molecular weight

  calculated average of about 8000 and a

active polymer of about 80%.

  Although the polyacetal carboxylates

  have been described above, it is obvious

  that they can be replaced in whole or in part

  by other polyacetal carboxylates of this type

  or adjuvant salts of organic detergents

  described in the aforementioned patents

  such compounds, their methods of

  brication and the compositions in which they

  are used. Also, the groups can be used

  described in the various patents, in particular the U.S.

  4,144,226, provided that they possess the static properties

  desired binders, which allow the aforementioned detergency builders to be depolymerized in acidic media, facilitating their biodegradation in the waste streams, but maintain their stability in alkaline media, such as

washing solutions.

  The bentonite used here is a colloidal clay (aluminum silicate) containing

  montmorillonite. The swelling bentonites are genera-

  typically characterized as so-

  diques, that is to say a bentonite in which the predominant cation is sodium. Among the clays

  of the sodium bentonite type, it is particularly preferable

  Wyoming (generally referred to as Western Bentonite from the United States of America or Wyoming). The swelling power of bentonite is

  usually associated with its softening properties

  tissue. In water, the swelling power of

  sodium bentonite is 3 to 20 milliliters / gram

  preferably 7 to 15 ml / gram, and its viscosity

  at a concentration of 6% in water, is generally

  preferably from 3 to 30 mPa.s, preferably from 8 to 30 mPa.s.

  Preferred swelling bentonites are sold under the trademark HI-JEL by Georgia

  Kaolin Co. These materials are the same as bentos

  which had previously been sold under the

  MINERAL COLLOID and THIXO-JEL. This

  are selectively exploited and encrusted bentonites

  and those considered to be most useful are available under the HI-JEL N 1, 2, 3, etc., names corresponding to THIXO-JEL N 1, 2, 3 and 4. These materials have a maximum moisture content free (before addition to the liquid medium) of 4% to 8% and densities of about 2.6. The bentonite is preferably a bentonite passing through a sieve with a mesh size of 0.074 mm, and more preferably at least 90% of the particles pass through a sieve with a mesh size of 0.044 mm.

  mm, so that the equivalent diameter of the bentonite

  can be considered as less than 74

  crometers, and more preferably below

cromètres.

  Chemical analyzes typical of

  bentonites that are useful for making

  The liquid dipters of the invention reveal that they contain from 64.8 to 73.0% SiO 2, from 14 to 18% Al 2 O 3, from 1.6 to 2.7% MgO, from 1.3 to 3, 1% of CaO, 2.3 to 3.4% of Fe 2 O 3, 0.8 to 2.8% of Na 2 O and

0.4 to 7.0% K20.

  Although western bentonites

  United States of America is preferred, it is also

  It is also possible to use other bentonites, such as those which can be made by treating Italian bentonites or the like containing relatively low proportions of exchangeable monovalent metals (sodium and potassium) with alkaline materials such as sodium carbonate. , in order to increase the cation exchange power of these products. It is considered that the Na20 content of the

  bentonite should be at least about 0.5%, preferably

  at least 1%, and better still at least

  2% so that the clay is sufficiently

  flante and has good softening properties

  and dispersants in aqueous suspension. Bentoni-

  Preferred blowing agents of the types described above are sold under the trade names Laviosa and Winkelmann, for example Laviosa AGB and Winkelmann.

G-13.

  Other bentonites that are particularly

  Useful in liquid detergent compositions of the invention because of their white or very light color include Polarite KB 325 from Amnerican Colloid Company, a California bentonite, and GK

  129 of Georgia Kaolin, a bentonite from Mexico.

  The viscosity of the liquid detergent of the

  vention is normally about 1000 to 10,000 mPa.s, preferably 2000 to 7000 mPa.s, but

  having other appropriate viscosities may also

  be useful. At the viscosity values mentioned

  liquid detergent can be poured, is stable, does not separate and is uniform. The pH of the liquid detergent suspension, generally from 7 to 11.5, preferably from 8 to 10.5, seems to favor the maintenance of the stability of the product and its suitability.

to be paid.

  The following non-limiting examples

  gloss the invention. Unless otherwise indicated, all

  parts are expressed in terms of weight and temperature.

erasures in C.

EXAMPLE 1

  Components Percent Pentasodium tripolyphosphate 11.0 Bentonite (GeorgiaKaolin 129) 12.0 Sodium carbonate 2.0 Sodium sesquicarbonate 2.0 (linear tridecyl) Sodium benzenesulfonate 8.0

AEOS (1) 3.0

  Carboxymethylcellulose (CMC) 0.2 Optical brightener 0.3 Fragrance 0.4 Enzyme (Esperase 8.0L) (2) 1.0 Glycerin 3.0 Borax 2.5 Citric acid 2.0

Water and additives the rest.

  (1) Sodium alkylpolyethoxysulfone in which the alkyl group has from 12 to 15 carbon atoms

  and the polyethoxy chain has 3 ethoxy groups.

  (2) "Esperase", sold by Novo Industries having an activity of 8.0 KNPU / g (Kilo-Novo protease units / g).

  The composition indicated above is pre-

  prepared by the following procedure: 30.0 parts of deionized water at 4.40C are added in a

  appropriate mixture such as a vertical cylindrical

  equipped with an agitator. By adjusting the stirrer to a medium degree of agitation, a mixture is incorporated

  consisting of 2.0 parts of anhydrous sodium carbonate, 2.0 parts of sodium sesquicarbonate and 0.2

  parts of sodium carboxymethylcellulose in water.

  The stirrer speed is then increased to a maximum value and 11.0 parts of pentasodium tripolyphosphate and 12.0 parts of bentonite are slowly added to the mixing apparatus over a period of 15 minutes to form a slurry. a dirty white. The stirring speed is then reduced to a slow / average value while adding 8.64 parts of a high content LTBS slurry (about 50%).

  IA (active ingredient). Then add the solution

  optical brightener and dye

  both in 0.3 part of Tinopal LMS-X (CIBA-GEIGY), 0.99 part of blue dye and 4.02 parts of water

  deionized. Once a solution has been

  their bluish green homogeneous, we add 0.4 part of

  perfume to the mixture with stirring. Then, we add

  3.0 parts of glycerine and 2.5 parts of

  rax as a two-component suspension. The stirring is continued until the mixture is

  of homogeneous appearance, then slowly add 2.0

  citric acid and 9.0 parts of water. We are

  then stirring the mixture, while adding

  , 95 parts of a detergent base of ingredients

  mixed media consisting of an LTBS suspension (envi-

  30% of AI) and AEOS (about 27.5% of AI). We

  then slowly add 1.0 part of proteolytic enzyme

  lytic while continuing the agitation until

  that all the materials are completely

persious or dissolved.

EXAMPLE 2

  Detergent compositions are formulated

  reinforced liquids A to G containing enzymes

  shown below in Table 1. The percentages

  The indicated values are expressed in percent by weight. The arrows are used to indicate the extent to which

  Compositions B to G are identical to Composite

A.

TABLE I

  Components Pentasodium tripolyphosphate Bentonite (Georgia-Kaolin 129) Sodium carbonate Sodium sesquicarbonate

(Linear tridecyl) benzene

sodium sulfonate

AEOS (1)

  Optical brightener (Tinopal LMS-X) Perfume CMC Enzyme (2) Glycerin Borax A 11.0 12.0 2.0 2.0 8.0 3.0 0.3 0.4 0.2 1.0 B -ICD -r 1 \ 11

3.0 - 3.0

- 2.5 2.5

G Ht

- - 3.0

- 2.5 2.5

- F

Carboxylic acid compound

Water and additives

- - - 2.0 2.0 2.0

to ---- the rest ------

  (1) Sodium alkylpolyethoxysulfone in which the alkyl group has from 12 to 15 carbon atoms

  and the polyethoxy chain has 3 ethoxy groups.

  (2) "Esperase" sold by Novo Industries with a

of 8.0 KNPU / g.

  The enzymatic activities of Compositions

  A to F are put to the test after 7 days of storage.

  at 43 C. The enzymatic activity measured for each

  - composition after this storage period is indi-

  Table II as a percentage of the initial value. The various carboxylic acids and salts used in the formulas of Compositions A, B, C, D, E and G are shown in Table II, and

  that the enzymatic activity corresponding to each

position.

TABLE II

ENZYMATIC STABILITY

  Composition P (dl A (Control) B (with glycerin) C (with borax) D (with glycerin and borax) Composition E (with carboxylic acid compound) the carboxylic acid compound being one of the following: ) Succinic acid (2) malonic acid (3) malic acid (4) tartaric acid (5) aspartic acid (6) citric acid with nzymatic activity at the end of 7 days at 43 C ND * ND ND ND il gi 'I II II (7) Sodium tartrate "(8) Sodium citrate

  * NA = not detectable (less than 10% residual activity)

  le) Composition G (with glycerol / borax / carboxylic acid compound),

  the carboxylic acid compound

  being one of the following- (1) succinic acid (2) malonic acid (3) malic acid (4) tartaric acid (5) aspartic acid (6) citric acid (7) sodium tartrate (8) citrate Sodium Percent Enzyme Activity After 7 Days at 43 C

  As shown in Table II, the Commission

  position A, the control composition, as well as the

  positions B and C which contain glycerin and borax, as respective individual stabilizers show almost no enzymatic activity at

  end of the 7-day storage period at 43 C.

  Since the enzymatic activities are lower than

  10% can not be accurately measured

  they are referred to as "ND". Composition D con-

  While the glycerin / borax in the absence of carboxylic acid compound exhibits an improvement in enzyme stability over Composition A, about 50% of the enzyme is deactivated. The various compositions E containing various compounds of the carboxylic acid type as indicated do not exhibit

  absolutely no improvement in enzymatic stability

  However, the G compositions formulated according to the invention exhibit the unexpected and synergistic improvement in stability.

  enzymatic, which is obtained by using a combination

  Glycerol / borax cation and a carboxylic acid compound in the liquid detergent compositions of the invention. We notice that each of

  compositions corresponding to Composition G manifests

  you have a clear increase in enzymatic activity

  compared to Composition D (containing glycerol

ne and borax).

  A comparison of the enzymatic activity obtained with the compositions D (glycerin / borax) and the various compositions F (borax / carboxylic acid compound) and G (formulated according to the invention)

  is shown below in Table III.

TABLE III

  Composition D (glycerin / borax) F (borax / malonic acid) G (glycerin / borax / malonic acid) F (borax / aspartic acid) G (glycerin / borax / aspartic acid) F (borax / citric acid) G (glycerin / borax / citric acid) Percent of enzymatic activity after 7 days at 43 C ND = not detectable (residual activity less than%).

  As shown in Table III, the differences

  its Compositions G containing a stabilizing system to

  three components according to the invention offer an improvement

  synergetic ratio of enzyme stability by

  Compositions D and F made according to the

anterior.

Claims (22)

  A stabilized reinforced liquid detergent composition containing enzymes and fabric softening, characterized in that it comprises: (a) about 5 to 20% by weight of one or more surfactant detergent compounds selected from the group consisting of   anionic, nonionic and ampho-   teria; (b) about 5 to 30% by weight of one or more   adjuvant salts of detergents chosen from tripoly-   alkali metal phosphates, the carbonates of   alkali levels, nitrilottiacetates of alkaline   lins and polyacetal carboxylates;   (c) about 5 to 20% by weight of a swelling clay   flante of the bentonite type; (d) an effective amount of an enzyme or enzyme mixture selected from alkaline protease and alpha-amylase enzymes;   (e) an enzyme stabilization system containing   on the basis of the weight of the detergent composition   (i) about 1 to 10% glycerin; (ii) approximately   1 to 8% of a boron compound selected from boiling acid   boric oxide and alkali metal borates   and (iii) about 0.5 to 8% of a compound of the type   carboxylic acid selected from mono-, di-   and / or polycarboxylic of 1 to 8 carbon atoms and their water-soluble salts; and (f) the remainder consisting of water and possibly in perfume and other additives.   2. Liquid detergent composition according to claim 1, characterized in that it comprises: (a) about 5 to 15% of an alkali metal alkylbenzene sulfonate in which the alkyl group has from 12 to 15 carbon atoms;   (b) about 0.5 to 5% of an alkylpolyethoxy sulphate   alkali metal fate in which the alkyl group   10 to 18 carbon atoms and the poly chain   ethoxy has 3 to 11 l ethylene oxide groups, the weight ratio of (a) to (b) being from about 2: 1 to about 6: 1;   (c) about 5 to 20% of sodium tripolyphosphate   dium; (d) about 1 to 10% of sodium carbonate, sodium bicarbonate or a mixture thereof, the weight ratio of (c) to (d) being from about 2: 1 to about 6: 1; (e) about 10 to 15% of a sodium bentonite; (f) an effective amount of said enzyme or enzyme mixture; (g) the enzyme stabilizer system containing, based on the weight of the detergent composition, (i) about 1 to 5% glycerin; (ii) about 1 to 1% of an alkali metal borate and (iii) about 0.5 to 4% of said carboxylic acid compound; and (h) the remainder consisting of water and possibly in minor additives.   3. Liquid detergent composition according to   Claim 2, characterized in that the alkylbenzene   alkali metal sulfonate is the (linear tridecyl   sodium benzenesulfonate and alkylpolyethoxy   The alkali metal salt is a sulphate of this type in which the alkali metal is sodium, the alkyl group contains from 12 to 15 carbon atoms and the   polyethoxy has about 3 oxide groups.   thylène. 4. Liquid detergent composition according to claim 3, characterized in that the ratio of tridecylbenzene sulfonate to polyethoxysulphate is from about 2: 1 to about 4: 1.   5. Liquid detergent composition according to claim 2, characterized in that the compound of   boron is an alkali metal borate.   Liquid detergent composition according to claim 5, characterized in that the borate is borax.   Liquid detergent composition according to claim 2, characterized in that it contains   about 8 to 16% of sodium tripolyphosphate and about   2 to 6% sodium carbonate, bicarbonate sodium or their mixtures.   8. liquid detergent composition according to claim 2, characterized in that the carboxylic acid compound is aspartic acid or a water-soluble salt of this acid.   9. Liquid detergent composition according to claim 2, characterized in that the carboxylic acid compound is tartaric acid or a water-soluble salt of this acid.   10. Detergent composition according to claim 2, characterized in that the carboxylic acid type is the acid water-soluble salt of this acid.   11. Detergent composition according to claim 2, characterized in that the carboxylic acid type is the acid a water-soluble salt of this acid.   12. Detergent composition according to claim 2, characterized in that the carboxylic acid type is the acid water-soluble salt of this acid.   liquid depending on whether the citric compound or a liquid depending on whether the malonic compound or liquid depending on whether the malic compound or a 13. A laundry process, characterized in that it consists in bringing the tissues into contact with each other.   stains and / or dirty to be washed with a de-   stabilized, stabilized, liquid-containing liquid containing enzymes, comprising: (a) about 5 to 20% by weight of one or more surface-active detergent compounds selected from   anionic, nonionic and amine detergent compounds   photères; (b) about 5 to 30% by weight of one or more   adjuvant detergency salts selected from tripolytics   alkali metal phosphates, alkali metal carbonates, alkali metal nitrilotriacetates and polyacetal carboxylates,   os05 (c) about 5 to 20% by weight of a flante of the bentonite type;   (d) an effective amount of an enzyme or a   enzyme mixture selected from alkaline enzymes of the protease and alpha-amylase type;   (e) an enzyme stabilization system containing   on the basis of the weight of the detergent composition   (i) about 1 to 10% glycerin, (ii) about 1 to 8% of a boron compound selected from boric acid, boric oxide, and alkali metal borates, and (iii) about 0.5 to 8% of a carboxylic acid compound selected from mono-, di- and / or polycarboxylic acids of 1 to 8 carbon atoms and their water-soluble salts, and (f) the remainder consisting of water and optionally in perfume and other additives.   14. The method of claim 13,   characterized in that the liquid detergent composition   comprises: (a) about 5 to 15% of an alkali metal alkylbenzene sulfonate wherein the alkyl group has from 12 to 15 carbon atoms;   (b) about 0.5 to 5% of an alkylpolyethoxy sulfa   alkali metal salt in which the alkyl group   from 10 to 18 carbon atoms and the polyetho-   xy has 3 to 11 ethylene oxide groups, the ratio   weight ratio of (a) to (b) being about 2: 1 to about viron 6: 1.   (c) about 5 to 20% of sodium tripolyphosphate   dium; (d) about 1 to 10% of sodium carbonate; sodium bicarbonate or mixtures thereof, the weight ratio of (c) to (d) being from about 2: 1 to about 6: 1; (e) about 10 to 15% of a sodium bentonite; (f) an effective amount of said enzyme or said enzyme mixture;   (g) the enzyme stabilization system con-   on the basis of the weight of the composition   (i) about 1 to 5% glycerin, (ii)   1 to 5% of an alkali metal borate and (iii)   0.5 to 4% of said carboxylic acid compound   lic; and (h) the remainder consisting of water and possibly in minor additives.   15. The method of claim 14,   characterized in that the metal alkylbenzene sulfonate   alkali is the (tridecyl linear) benzene-sulpho   sodium nate and metal alkylpolyethoxy sulfate   alkali is a sulphate of this type in which the   alkali is sodium, the alkyl group has 12 to 15 carbon atoms and the polyethoxy chalne   has about 3 ethylene oxide groups.   16. The method of claim 15,   characterized in that the ratio of tridecylbenzene   Polyethoxy sulphate sulphonate is about 2: 1 a about 4: 1.   17. The method of claim 14,   characterized in that the boron compound is borax.   18. The method of claim 14,   characterized in that the liquid detergent composition   contains about 8 to 16% sodium tripolyphosphate and about 2 to 6% sodium carbonate,   sodium bicarbonate or their mixtures.   19. The method of claim 14,   characterized in that the carboxylic acid type compound   xyl is aspartic acid or a water-soluble salt of this acid.   20. The method of claim 14,   characterized in that the carboxylic acid type compound   xyl is citric acid or a water-soluble salt of this acid.   21. The method of claim 14,   characterized in that the acidic acid compound   Boxylic acid is malic acid or a water-soluble salt of this acid.   22. The method of claim 14,   characterized in that the acidic acid compound   boxylic acid is malonic acid or a hydrosolu ble of this acid.