FR2585363A1 - STABILIZED REINFORCED LIQUID DETERGENT COMPOSITION CONTAINING ENZYMES, AND WASHING METHOD EMPLOYING SAME - Google Patents

Abstract

THE INVENTION RELATES TO A STABILIZED REINFORCED LIQUID DETERGENT COMPOSITION CONTAINING ENZYMES. THE SAID COMPOSITION CONTAINS DETERMINED PROPORTIONS OF SURFACE-ACTIVE DETERGENT COMPOUNDS, ADJUSTING SALTS OF DETERGENCE, ENZYMES OR MIXTURE OF ENZYMES, AN ENZYME STABILIZATION SYSTEM CONTAINING DETERMINED PROPORTIONS OF GLYCERINE AND COMPOUND CONSISTS OF CARBOXYLIC ACID, 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-

  apply the protein and amylaceous materials that are

  soil tissue, which facilitates the elimination of

  stains, for example sauce stains, blood stains, chocolate stains, etc., during laundering. However, enzymatic materials suitable for laundry compositions, in particular

  particularly proteolytic enzymes, are relatively

  expensive. In fact, they are among the

  most expensive ingredients of a detergent composition

  conventional liquid, even if they are pre-

  in relatively minor quantities. In addition, the enzymes are known to be unstable in aqueous compositions. This is the reason why it is usually necessary to use an excess of enzymes in liquid detergent formulations

  to compensate for the expected loss of enzyme activity

  for extended periods of storage.

  Therefore, the prior art abounds in

  proposals for stabilizing the deter-

  containing enzymes, and in particular

  Use the unreinforced liquid compositions using various materials that 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 relatively

  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,

  relatively large amounts of glycerol are required to stabilize the enzymes of the composition. However, as demonstrated hereinafter, the stabilizing effect of the enzymes 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

  under N 0126505, a detergent composition is described.

  an aqueous liquid containing enzymes and containing an enzyme stabilizing mixture, consisting of

  certain dicarboxylic acids and borax. Acids

  dicarboxylic acids are recommended as a substitute for a polyol such as glycerol in known stabilizer mixtures of the enzymes glycerol and a boron compound. However,

  dicarboxylic acid-borax mixtures of this

  The above-mentioned mixture of glycerin and borax provides at most a moderate stabilizing effect in the compositions.

  reinforced liquid detergents of the present invention.

  tion. It is therefore necessary to strongly improve the

  stability of the enzymes of detergent compositions

  reinforced water types of the type defined here, to a much greater extent than

current state of the art.

  The present invention provides a composi-

  stabilized, liquid stabilized liquid detergent composition comprising: (a) from 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 detergency salts chosen from

  lyphosphates of alkali metals, carbonates of

  alkali levels, the nitrilotriacetates of alkaline

  lins and polyacetal carboxylates; (c) an effective amount of an enzyme or enzyme mixture selected from alkaline protease and alpha-amylase enzymes;

  (d) 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 (e) the remainder consisting of water and possibly

in perfume and other additives.

  In a preferred embodiment of

  the invention, the liquid detergent composition comprises

  takes: (a) about 5 to 15% of an alkali metal alkylbenzene sulfonate wherein the alkyl group contains from 12 to 15 carbon atoms; (b) about 2 to 5% of an alkali metal alkyl polyethoxy sulfate in which the alkyl group contains from 10 to 18 carbon atoms and the polyithoxy chain has from 3 to 11 ethylene oxide groups, the ratio of the weight of (a) a (b) being from about 2: 1 to about 8: 1;

  (c) about 5 to 20% of sodium tripolyphosphate

  dium; (d) about 1 to 10% sodium carbonate, the weight ratio of (c) to (d) being from about 2: 1 to about 6: 1;

  (e) an effective amount of the enzyme or

age of aforesaid enzymes;

  (f) an enzyme stabilization system that contains

  on the basis of the weight of the detergent composition

  (i) about 3 to 7% glycerin, (ii) about 1 to 5% of an alkali metal borate, and (iii) about 0.5 to 4% of said carboxylic acid compound; and

  (g) 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 the

  bringing these materials into contact with an aqueous solution

  liquid detergent compositions defined below.

above.

  The liquid detergent described is a deter-

  for heavy laundering work, accepting

  table for commercial purposes, able to clean

  laundry with both soil and

  oily and particulate matter. In addition, composi-

  described can be used for pre-training.

  very dirty parts, such as collars and

wrists of washing articles.

  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

  rax, either by the mixture of borax and dicarboxylic acid

  when used independently of each other.

  the other as enzyme stabilizers. For purposes of

  mercury, a desirable enzyme stability corresponding to

  usually lays about a half-life of a week

at a temperature of 43 C.

  The enzyme stabilization system of the invention is a mixture of glycerin, a boron compound selected from boric acid, boric oxide and an alkali metal borate and a compound of the type

  carboxylic acid, as defined herein. The weight of the system

  stabilizer contained in the deter-

  The present invention provides, in general, about 3 to 25%, preferably about 6 to 15%, by weight of these compositions. The report

  weight of glycerin to borax mixtures of stabi-

  is typically about 1 to 3. It is

  preferred glycerine in the composition is

  3 to 7%, the preferred amount of boron compound

  is about 1 to 5%, and the preferred amount of

  carboxylic acid is approximately 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 hydrogen substituents

  xy or amino, such as malic acid

  (HOOCCHOHCH2COOH), tartaric acid (dihydroxy acid

  succinic acid), aspartic acid (amino-succinic acid)

  that) and citric acid. Carboxylic acids

  preferred embodiments of the invention are succinic acid,

  maleic acid, malonic acid, and malic acid.

  From a commercial point of view, a carboxylic acid

  particularly preferred is citric acid and / or its

  salts because of their taken relatively low.

  The alkaline proteolytic enzymes con-

  coming from the compositions of the present invention

  take the various liquid enzymatic preparations

  of trade 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 are

  less convenient to incorporate into the compositions

  reinforced liquid tergents. Thus, preparations

  Suitable liquid enzymatic enzymes include "Alcala-

  "and" Esperase ", sold by Novo Industries, Copen-

  hague, Denmark, and "Maxatase" and "AZ-Protease" sold

by Gist-Brocades, Delft, The Netherlands.

  Among the liquid enzymatic preparations

  Suitable α-amylase-type

  sold by Novo Industries and Gist-Brocades under

  the trademarks "Termamyl" and "Maxamyl",

tively.

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

  optimized activity at the higher pH values cor-

  corresponding to the reinforced detergent compositions.

  The preferred detergents for use in the liquid compositions of the invention are the synthetic anionic detergent compounds,

  -. and in particular a mixture of (higher alkyl) benzene-

  sulfonate and alkyl-polyethoxy-sulfate. Although the formulas of the present invention may also contain other water soluble (higher alkyl) benzene sulfonates, for example potassium salts and,

  in some cases the ammonium or alkanol

  monium, where appropriate, it has been found that the sodium salt is the preferred one, which is also the case with respect to the

  alkylpolyethoxy sulfate detergent. The alkyl benzene

  sulfonate is that in which the higher alkyl group

  has from 12 to 15 carbon atoms, preferably

  13 carbon atoms. The alkyl polyethoxy sulfate,

  which can also be designated. like a linear alcohol

  sulfated polyethoxylated higher grade or the product of

  sulphated densification of a higher fatty alcohol and of ethylene oxide or of polyethoxylene glycol, is that in which the alkyl group comprises from 10 to 18 carbon atoms, preferably from 12 to 15 carbon atoms,

  for example about 13 carbon atoms, and which

  from 3 to 11 ethylene oxide groups, preferably

  this is from 3 to 7, more preferably from 3 to 5, and in particular 3 or about 3 ethylene oxide groups. The ratio of alkylbenzene sulfonate to polyethoxysulfate in the detergent mixture is preferably about

  2: 1 to 8: 1, and more preferably about 3: 1 to 5: 1 by weight.

  At ratios greater than 5: 1, physical stability

  product may be adversely affected.

  In appropriate cases, other deter-

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

  monoglyceride sulphates, sarcosinates and dithers

  similar function, preferably in the form of

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

  sodium) and contain fatty alkyl groups or

  long chain neogen (8 to 20 carbon atoms).

  In addition to any additional synthetic anionic organic detergents, nonionic and amphoteric materials may also be present, such as Neodol (R), sold by Shell Chemical Company, which are condensation products of ethylene oxide and fatty alcohols. higher, for example Neodol (Ry 23-6.5, which is a condensation product of a higher fatty alcohol of about 12 or 13 carbon atoms with about 6.5 moles of ethylene oxide.) Examples of the various detergents and various classes of detergents mentioned can be found in Surface Active Agents,

  Flight. II, Schwartz, Perry and Berch (Interscience Pu-

blishers, 1958).

  The combination of adjuvant salts of deter-

  of the present invention, which has proved to be

  required to improve the detergency of the mixture of

  synthetic organic anionic detergents and

  The desired pH in the liquid detergent and in the wash water is a mixture of sodium tripolyphosphate and sodium carbonate. The detergency builder salts are used in the compositions of the present invention in generally

  from about 5 to 25% by weight. In the combination

  of adjuvant detergency salts, the tripoly-

  sodium phosphate is present in proportions of

  5 to 20%, preferably 10 to 16%, and the sodium carbonate is present in an amount of about 1 to 10% by weight, preferably 3 to 7%, the ratio of

  weight of carbonate tripolyphosphate in

  Preferred detergency builders are about 2: 1 to 6: 1, and more preferably about 2: 1 to 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

  treatment, easier mixing and a better

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

  Phase I type tripolyphosphate.

  the tripolyphosphate content of the Phase I

  is less than 30% of the tripolyphosphate used.

  Although in some cases it is possible to use

  incompletely neutralized polyphosphate, phosphate

  that we use can normally be considered

  me being pentasodium tripolyphosphate Na5P3010.

  Of course, in some cases, for example

  potassium salts or other materials, the

  mutual storage of ions in an aqueous medium may give salts other than sodium tripolyphosphate, but for the purpose of this specification it is considered that the

  sodium tripolyphosphate, in the form of pentaso-

  which is the material normally introduced into the mixer to produce 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

  tioned. However, the tripolyphosphate-carbon mixture

  Although the other detergency builders and their mixtures are also usable, it has been shown to be the most advantageous. Other detergency builders that can be used as supplements, in addition to the proportions of the detergency builders mentioned above, include other phosphates.

  such as tetrasodium pyrophosphate or pyrophosphate

  - Tetrapotassium phate, sodium bicarbonate, sodium citrate, sodium gluconate, sodium silicate, and sodium sesquicarbonate. From

  water-insoluble detergency builders that can

  zeolites, such as Zeolite A, usually in the form of its crystalline hydrate, although amorphous zeolites

can also be useful.

  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.

  Polyacetal carboxylates that are useful

  here as detergency builders can be considered

  res as being those described in the U.S.A.

  No. 4,144,226 and they may be prepared by the procedure

  mentioned in it. An example of such a product is represented by the formula: R 1 - (CHO) n - R 2 COOM where M is selected from an alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms,

  tetraalkylammonium groups and alkanolamines

  these last two types of groups having from 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 against rapid depolymerization

  in alkaline solution. Preferably, the polyacetal

  carboxylate is the one in which M is a metal

  calin, for example sodium, n ranges from 50 to 200, R is

CH3CH2? MOOC

CH3CH2,

* HCO- or H3C-CO-

I

H3C MOOC

  or a mixture of these groups, R2 is

OCH2CH3

  And CH CH3 and n 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 better still from 5000 to 9000, for example

about 8000.

  A polyacetal sodium carboxylate parti-

  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 may be replaced in whole or in part by other polyacetal carboxylates of this type or

  related organic detergency builder salts

  cited in the aforementioned patents relating to such compounds, their manufacturing processes and

  the compositions in which they are used.

  Also, termination groups can be used

  described in the various patents, in particular

  U.S. Patent No. 4,144,226, provided that they possess the desired stabilizing properties, which allow the detergency builders mentioned

  to be depolymerized in acidic media, easily

  their biodegradation in residual currents

  res, but maintain their stability in

  alkalis, such as washing solutions.

  The only other necessary component of the

  Liquid tergents of the invention is water. normally

  the hardness of this water is less than about 300 ppm as CaCO3, and preferably

  is less than 150 ppm. It can often be desirable

  table to use deionized water, although city water, hardness less than 50 or 100 ppm,

  is often just as satisfying.

  Various additives may be present in

  liquid detergents, such as fluorescers,

  cents of brightening, perfumes and dyes. Fluorescent brighteners include derivatives

  well known stilbene, including

  Cotton and nylon, for example those sold under the trademark Tinopal (5BM Conc.). The perfumes that are used generally include essential oils, esters, aldehydes and /

  or alcohols, all of which are known in the art of

  den. The dyes may include dyes

  res and dispersible pigments in various water

  types, including ultramarine blue. Salts of char-

  minerals, such as sodium sulphate and chlo-

  sodium chloride, may be present, as may

  anti-redeposition agents such as carboxymethylcellulose

  sodium lulose; dispersants such as sodium polyacrylate; bleaching agents;

  bactericides, fungicides; anti-agents

  foam such as silicones; anti-fouling agents

  such as copolyesters; preservatives such as formalin; foam stabilizers such as myristic lauric diethanolamide; and

  auxiliary solvents such as ethanol. normally

  The individual proportions of such additives are less than 3%, often less than 1% and sometimes even less than 0.5%, with the exception of

  fillers and solvents, and other detergents and

  detergency drinkers for which the proportions

  can sometimes be as high as 10%. The pro-

  total portion of additives, including synthetic detergents and non-detergency builders,

  does not represent more than 20% of the product, and

  happily less than 10%, better still less than 5%.

  Obviously, the additives used are chosen from

  not to disturb the washing action of the detergent

  liquid and avoid the instability of the product at rest. Also, the additives that are the cause of

  unwanted deposits on the linen are to be avoided.

  The liquid compositions of the invention are effective and easy to use. comparatively

  detergent powders for heavy laundering

  wise, much smaller volumes of

  of the present invention to achieve a comparable cleaning of soiled laundry. For example, in

  using a preferred formulation typical of the pre-

  invention, it should only be about 132 grams or

  a 1/2 cup of liquid for a full tank of

  a top-loading automatic washing machine in which the volume of the water is 57 to 68 liters; and it takes even less for them

  front loading machines. Thus, the concentration

  of the liquid detergent composition in

  the wash water is of the order of about 0.2%. Habi-

  the proportion of the liquid composition in the wash solution is between

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

  The proportions of the various constituents of the

  liquid phase may vary accordingly. Equivalent results can be obtained by using

  larger proportions of a more dilute formulation

  but the larger amount needed

  extra packaging and is less convenient to use.

  by the consumer and can also lead to

a separation of the product.

  The viscosity of the liquid detergent of the

  vention is normally about 1000 to 10,000 mPa.s, preferably 2000 to 5000 mPa.s, but the products

  having other appropriate viscosities may also

  be useful. At the viscosity values mentioned, the liquid detergent can be poured, it is stable,

  does not separate and is uniform. The pH of the suspension

  liquid detergent, usually from 7 to 11.5,

  preferably from 8 to 10.5, seems to favor the

  the stability of the product and its suitability for

  The following nonlimiting examples illustrate

  the invention. Unless otherwise indicated, all

  the parts are expressed in weight and the temperatures are

res in C.

EXAMPLE 1

  Components Percent Pentasodium Tripolyphosphate 15.0 Sodium Carbonate 5.0

  (Linear tridecyl) benzene-sulfo

sodium nate 12.2

AEOS (1) 2.8

  Carboxymethylcellulose (CMC) 0.15 Optical brightener 0.4 Fragrance 0.3 Enzyme (Esperase 8.0L) (2) 1.0 Glycerin 4.0 Borax 3.0 Triethanolamine 1.0 Sodium citrate 2.0

Water and additives the rest.

  (1) Sodium alkylpolyethoxysulfide in which the

  alkyl group has from 12 to 15 carbon atoms

  bone and the polyethoxy chain has 3 ethoxy groups. (2) "Esperase", sold by Novo Industries having an activity of 8.0 KNPU / g (Kilo-protease units)

Novo / g).

  The composition indicated above is pre-

  prepared by the following procedure: 32.5 parts of deionized water are added to a mixing apparatus

  such as a vertical cylindrical tank equipped with

  from an agitator. By adjusting the stirrer to a medium degree of stirring, a mixture consisting of 5.0 parts of anhydrous sodium carbonate and 0.17 parts of water is added.

  part of sodium carboxymethylcellulose in water.

  The stirrer speed is then increased to a maximum value and 15.0 parts of pentasodium tripolyphosphate are slowly added to the mixing apparatus over a period of 10 to 15 minutes to form a milky white suspension. The stirring speed is then reduced to a slow / average value while adding 19.1 parts of an LTBS suspension to

  high content (about 50%) of AI (active ingredient).

  The optimum brightener solution is then added.

  that and dye consisting of 0.4 part of Tin-

  pal LMS-X (CIBA-GEIGY), 0.06 part blue dye and 2.0 parts deionized water. As soon as a homogeneous blue solution was obtained, 0.3 parts of perfume were added to the stirring mixture. Then, slowly add 4.0 parts of glycerin, 3.0 parts

  of borax and 1.0 part of triethanolamine (the

  long-term product stability) in the form of

  a three-component suspension. We continue to

  until the mixture is homogeneous,

  then 2.0 parts of sodium citrate are slowly added.

  dium and 4.0 parts of water. The agitation is then reduced

  mixture while adding a detergent base of mixed active ingredients consisting of 5.7 parts

  of suspension of TLBS (approximately 50% AI) and 4.7

  of AEOS (about 60% of AI). Then add

  1.0 part proteolytic enzyme with stirring

  until all the materials are

  completely dispersed or dissolved.

EXAMPLE 2

  The detergent compositions are

  strengths A to G containing enzymes as

  shown below in Table 1. The percentages

  they are expressed in percent by weight. The arrows

  used to indicate the extent to which composi-

  B to G are identical to Composition A.

TABLE 1

  Components A B C D E F G Pentasodium tripolyphosphate 15% Sodium carbonate (anhydrous) 5%

(Linear tridecyl) benzene

sodium sulfonate 12.2

AEOS (1) 2.8

  Optical Brightening Agent (Tinopal LMS-X) 0.4 Fragrance 0.3

CMC 0.2

  Enzyme (2) 1 Glycerin - 4- 4 - - 4 Borax - - 3 3 - 3 3 Carboxylic acid Water and additives

2-- 2 2

to - 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 having a

activity of 8.0 KNPU / g.

  The enzymatic activities of

  A to G are tested after 7 days of storage at 43 C. The enzymatic activity measured

  for each composition after this period of

  posage is shown in Table II and in Table II.

  III 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 as well as

  the enzymatic activity corresponding to each

tion.

TABLE II

ENZYMATIC STABILITY

  Composition Pou enz of 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) Oxalic acid (5) Maleic acid (6) Recent tartaric acid activity after 7 days at 43 C NDX ND ND ND II! It I. (7) Aspartic Acid (8) Citric Acid (9) Glycine (10) Alanine (11) Sodium Succinate (12) Sodium Formate (13) Sodium Acetate (14) Sodium Tartrate (15) Citrate of sodium (16) Sodium glycolate (17) Sodium tetrahydroxysuccinate I n I nn I ND = Not detectable (lower residual activity%). Composition G (with glycerin / borax / carboxylic acid-type compound), enzymatic after the 7-carboxylic acid compound at 43 ° C being one of the following: (1) Sodium succinate 60 (2) ) Succinic acid 94 (3) Malonic acid 91 (4) Malic acid 79 (5) Oxalic acid 81 (6) Maleic acid 88 (7) Tartaric acid 63 (8) Aspartic acid 84 (9) Citric acid 62 (10) Glycine 80 (11) Alanine 79 (12) Sodium formate 57 (13) Sodium acetate 50 (14) Sodium tartrate 54 (15) Sodium citrate 57 (16) Sodium glycolate 50 (17) Sodium tetrahydroxy succinate 61

  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, respectively, as well as stabilizers

  have almost no enzyme activity.

  at the end of the 7-day storage period

  at 430C. Since the enzymatic activities in-

  Below 10% can not be accurately measured, they are referred to as "ND". Composition D containing glycerine / borax in the absence of carboxylic acid compound shows an improvement in enzyme stability compared to the compositions

  A, B and C, but more than 50% of the enzyme is deactivated.

  ved. The various Compositions E containing various coma

  carboxylic acid type as indicated does not pre-

  feel absolutely no improvement in enzyme stability compared to Compositions A, B and C.

  However, the G Compositions formulated according to the invention

  the unexpected and synergistic improvement in enzyme stability, which is achieved using a combination of glycerin / borax and a

  carboxylic acid type in the detergent compositions.

  liquids of the invention. We notice that among the

  17 compositions corresponding to the Composition G testers

  the enzymatic activity is improved compared with

  to Composition D (containing glycerin and borax).

  A comparison of the enzymatic activity obtained with the compositions D (glycerin / borax) and

  the various F Compositions (borax / acid-type compound

  carboxylic acid) and G (formulated according to the invention) is

shown below in Table III.

TABLE III

ENZYMATIC STABILITY

  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 430C ND * = ND = undetectable (residual activity less than

10%).

  As shown in Table III, the differences

  its Compositions G containing a stabilizing system to

  three components according to the invention provides an improvement.

  synergistic effect of enzymatic stability with respect to compositions D and F formulated according to the prior art.

Claims (22)

  A stabilized reinforced liquid detergent composition containing enzymes, 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 detergency salts selected from   lyphosphates of alkali metals, carbonates of   alkali metals, nitrilotriacetates of   hollies and polyacetal carboxylates; (c) an effective amount of an enzyme or enzyme mixture selected from alkaline protease and alpha-amylase enzymes;   (d) 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 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. carbon and their water-soluble salts; and (e) 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 2 to 5% of an alkali metal alkyl polyethoxy sulfate in which the alkyl group has 10 to 18 carbon atoms and the polyethoxy chain has 3 to 11 ethylene oxide groups, the ratio of weight of (a) to (b) being from about 2: 1 to about 8: 1;   (c) about 5 to 20% of sodium tripolyphosphate   dium; (d) about 1 to 10% sodium carbonate, the weight ratio of (c) to (d) being from about 2: 1 to about 6: 1; (e) an effective amount of said enzyme or enzyme mixture; (f) the enzyme stabilizer system containing, based on the weight of the detergent composition, (i) about 3 to 7% glycerin, (ii) about 1 to 5% of an alkali metal borate, and (iii) about 0.5 to 4% of said carboxylic acid compound; and (g) 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 the alkylpolyethoxy sulphate   alkali metal fate is a sulfate of this type in which the alkali metal is sodium, the alkyl group   contains 12 to 15 carbon atoms and the poly-   ethoxy has about 3 ethylene oxide groups.   4. Liquid detergent composition according to claim 3, characterized in that the ratio of tridecylbenzene sulfonate to polyethoxysulphate is from about 3: 1 to about 5: 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 10 to 16% of sodium tripolyphosphate and   viron 3 to 7% sodium carbonate.   8. liquid detergent composition according to claim 2, characterized in that the carboxylic acid compound is succinic 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 maleic acid or a salt water soluble of this acid.   10. Liquid detergent composition according to claim 2, characterized in that the carboxylic acid compound is citric acid or a salt water soluble of this acid.   11. Liquid detergent composition according to claim 2, characterized in that the carboxylic acid compound is malonic acid or a salt. water soluble of this acid.   12. liquid detergent composition according to claim 2, characterized in that the carboxylic acid type compound is malic acid or a salt water soluble of this acid.   13. A laundry process, characterized in that it consists in contacting the stained tissue   and / or dirty to wash with a detergent composition   stabilized reinforced protein containing enzymes,   taking: (a) about 5 to 20% by weight of one or more surfactant detergent compounds selected from   anionic, nonionic and ampho-   defects; (b) about 5 to 30% by weight of one or more   adjuvant detergency salts selected from   lyphosphates of alkali metals, carbonates of   alkali levels, the nitrilotriacetates of alkaline   lins and polyacetal carboxylates; (c) an effective amount of an enzyme or   enzyme mixture selected from alkaline enzymes   protease and alpha-amylase type;   (d) an enzyme stabilization system containing   containing, on the basis of the weight of the composition de-   tergente, (i) about 1 to 10% glycerin, (ii)   1 to 8% of a boron compound selected from the group consisting of   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 compounds of 1 to 8 carbon atoms   ne and their water-soluble salts; and (e) the remainder consisting of water and possibly 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 2 to 5% of an alkali metal alkylpolyethoxy sulfate in which the alkyl group has 10 to 18 carbon atoms and the polyethoxy chain has 3 to 11 ethylene oxide groups, the weight ratio of (a) to (b) being from about 2: 1 to about 8: 1;   (c) about 5 to 20% of sodium tripolyphosphate   dium; (d) about 1 to 10% sodium carbonate, the weight ratio of (c) to (d) being from about 2: 1 to about 6: 1; (e) an effective amount of said enzyme or enzyme mixture;   (f) the enzyme stabilization system con-   on the basis of the weight of the composition   and (iii) about 0.5 to 4% of said carboxylic acid compound; and (g) the remainder consisting of water and possibly minor additives.   15. The method of claim 14,   characterized in that the metal alkylbenzene sulfonate   alkali is the (linear tridecyl) benzene-sulfo   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 chain   has about 3 ethylene oxide groups.   16. The method of claim 15,   characterized in that the ratio of tridecylbenzene   Polyethoxy sulphate sulphonate is approximately 3: 1 to about 5: 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 10 to 16% tripolyphosphate   sodium and about 3 to 7% of sodium carbonate.   19. The method of claim 14,   characterized in that the carboxylic acid type compound   xyl is succinic 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 carboxylic acid type compound   xyl is maleic acid or a water-soluble salt of this acid.   22. The method of claim 14,   characterized in that said acidic acid compound   boxylic acid is malonic acid or a hydrosolu ble of this acid.