FR2677371A1 - CONCENTRATED LIQUID DETERGENT COMPOSITION CONTAINING POLYPHOSPHONATE SEQUESTERANT. - Google Patents

Abstract

The present invention relates to a concentrated liquid detergent composition - water content <= 10% by weight - which contains a polyphosphonate type sequestering agent.

Description

Detergent composition Concentrated liquid containing an agent

  sequestering polyphosphonate type.

  The present invention relates to the field of

  liquid detergent, for washing clothes, especially in washing machines. More specifically, it relates to a composition

  concentrated liquid detergent containing at least one polyphosphoric acid

nate as a sequestering agent.

  By "concentrated liquid detergent compositions"

  designates in this description and the claims that

  follow liquid detergent compositions not containing more

10% by weight of water.

  Liquid detergents have grown considerably

  in recent years for a variety of reasons.

  their easier dissolution in washing baths, their handling

  Easier lation especially for their dosage and pretreatment

stain.

  However, it has become more and more desirable to have liquid detergent compositions concentrated both for economic reasons (valorization of the linear space of the dispenser, reduction of production and energy costs for the producer, etc.), practical (saving space for storage and use) and ecological (reduction in packaging rejects, reduction of organic

surface, etc.).

  The making of such low water liquid detergent compositions which are both efficient, stable and sufficiently concentrated to provide the advantages enumerated above has not been evident; the difficulty was particularly increased when it was desired to concentrate the active ingredients commonly used in liquid detergents according to the prior art-not concentrated

  within the meaning of the invention and use at least one sequestering agent.

  It is well known, both by those skilled in the art and by the user, that commercially available liquid detergents suffer from a lower performance compared to detergent powders on certain types of very specific stains, such as: coffee, wine , tea, fruit juice, etc., called bleachable stains. This relative deficiency is largely related to the absence of oxidizing bleaching agent in the liquid detergent compositions. It has indeed been found that even if it is possible to stabilize such a peroxidizing agent in a manner which is approximately aqueous or non-aqueous formula - which implies in any case packaging and especially special and expensive plugs, it is virtually impossible to incorporate enzymes stably in these compositions, these

  being almost immediately degraded.

  It is therefore desirable, insofar as the liquid detergents do not contain whitening agents, to incorporate a system of agents for sequestering di- and trivalent cations (in particular

M + ++ +++

  particular cations such as: Ca, Mg, Fe, etc.).

  Such systems can in fact largely compensate for the loss of performance inherent in the absence of peroxidative bleaching agents by acting on the bleachable stains by their direct effects (breaking of the fiber-fouling bonds).

  and indirect (prevention / peptization of insoluble complexes).

  Cations, such as Ca ++ and Mg ++, present in the washing bath which come either from the washing water, or from the stains of the clothes to be washed, are detrimental to the washing performance of the detergent compositions. origin of the formation of insoluble complexes which are deposited either on the elements of the washing machine or on the cloth and then give it a gray appearance The said complexes result from interactions between the said cations and the surfactants and / or

  soaps present in the detergent composition.

  Sequestering agents prevent the formation of such complexes They also have a direct effect on the removal of stains, cutting the bonds that can form between

  certain types of soiling and textile fibers; linkages

  thanks to Ca, Mg, Fe bridges.

  Among the main sequestering agents used in the detergent compositions of the prior art, there may be mentioned polyphosphonates, which have a certain interest.

  because of their effectiveness, even at relatively low rates.

  so-called polyphosphonates have the property of adsorbing on the surface

  soil particles by giving them negative charges.

  The recoalescence of the said particles at the origin of their

  Redeposition on the fibers is thus avoided.

  The polyphosphonates generally used in

  liquid or pulverulent detergent positions are the alkali metal, ammonium, alkanolamine or alkaneamine salts of polyphosphonic acids such as, for example, the amino acid

  tri (methylene phosphonic); ethylenic acid diamino tetra-

  (methylene phosphonic); hexamethylene diamino tetra-

  (methylene phosphonic acid) or diethylenic triamino penta

(methylene phosphonic).

  The use of 1-hydroxy-ethane-1,1-diphosphoric acid

  (HEDP) and its salts, as a sequestering agent, in powder detergents only, has also been described in

EP-A-0291 869.

  However, the use of said polyphosphonates and particularly that of HEDP, as sequestering agent, in the detergent compositions of the invention-whose water content is less than or equal to 10% did not result from an obvious step, insofar as solubility problems have been encountered. Indeed, when attempts have been made to incorporate such sequestering agents, and especially the sodium salts of HEDP alone or in combination with other phosphonates in detergent compositions with low water content, it has generally appeared , more or less long term, a precipitate, unacceptable commercially and likely to alter the

washing performance.

  The Applicant then found that it is possible to

  surprisingly, to incorporate, in a stable way, polyphosphonophosphorus

  in concentrated liquid detergent compositions, provided that they are in the form of simple salts or of mixed, specific salts Details are given more

  before on the nature of said salts and their method of preparation.

  Moreover, it has been found that other conditions

  should be respected, as to the nature and quantity of

  vention of active ingredients, to obtain compositions

  concentrated, stable, homogeneous, effective liquid detergents.

  In particular, it appeared necessary that the said

detergent

  contain at least 30% by weight of saturated fatty acids

  re (s) and unsaturated (s), said (s) unsaturated fatty acid (s) being present (s) at a rate of 6 to 10% by weight of the overall composition; and that these saturated (and unsaturated) fatty acids, as well as the anionic surfactants involved, are, within

  said compositions in a neutralized, non-arbitrary form.

  The formulations developed by the Applicant are specified below. They contain: at 20% by weight (expressed as active acid) of at least one anionic surfactant, preferably from 15 to 20% by weight, at 40% by weight of at least one nonionic surfactant, at 40% by weight (expressed as active acid) of saturated and unsaturated fatty acids, the unsaturated fatty acid (s) (s) ) being present in a proportion of 6 to 10% by weight of the total composition, 0.5 to 6% by weight (expressed as active acid) of at least one polyphosphonate sequestering agent, in the form of a salt: simple potassium, ammonium, a C 2 -C 8 alkanolamine or a C 2 -C 8 alkaneamine; or

  mixed with an alkali metal, ammonium, alkanol

  a C 2 -C 8 mine or a C 2 -C 8 alkaneamine, on the one hand, and an alkaline earth metal, on the other hand; said anionic surfactant (s) and fatty acids having been previously neutralized or neutralized in situ by at least one neutralizing agent selected from alkanolamines,

  C 2 -C 8 and alkaneamines C 2 -C 8.

  Details of each of the constitutions are given below.

  killing compositions of the invention.

  As anionic surfactants, it is possible to use the agents known to fulfill this function in the liquid liquors of the prior art, and in particular: alkylbenzenesulfonates whose straight or branched chain alkyl groups contain about 10 to 16 carbon atoms; alkyl or alkenyl ether sulphates with straight or branched chain alkyl or alkenyl groups containing about 10

  to 20 carbon atoms and from about 0.5 to 8 moles of

  ethylene oxide, for example ethylene oxide, propylene oxide, butylene oxide or a mixture of oxides; alkyl or alkenyl sulphates with straight or branched chain alkyl groups having from about 10 to about 22 carbon atoms; alkanesulfonates having about 10 to 22 carbon atoms; alkyl or alkenylphosphates of formula:

O

  II (R 10) m P (OX) in which: R 1 is a linear or branched alkyl or alkenyl group having from approximately 8 to 22 carbon atoms, optionally substituted on the main carbon chain by one or more halogen or phenyl radicals and / or possibly interrupted by a group such as: o He

O C -,

0 O R R O O O

He -Il 12 N 2 he

C 0 -, C N -, N C -, C NH -, NH C-,

  0-, + X is an alkali metal cation, NH 4 or an amine cation; m and N are integers different from zero and m + N = 3, m is 1 or 2; α-olefin sulfonates having about carbon atoms; the "sulphonated" fatty acids and their esters respectively with the formulas:

R 1 CH C

s 03 XXx and

of alkanol

such as to 22 responding

R CH C I \

503 X O R 2

  in which: R 1 and X are as defined above; R 2 is a linear or branched alkyl or alkenyl group comprising from 1 to 10 carbon atoms or a group resulting from the condensation of ethylene oxide: that is to say a group of formula - (CH 2 CH 2 0) nH o N is an integer from 1 to about 15;

  soluble salts of sulfates or sulpho

  N-alkylamide fatty acid esters having the formulas

after:

O R 'O R'

  in which: R 1 and X are as defined above, and wherein R 1 and X are as defined above; R'2 is hydrogen or a group as defined above for R 2; R'3 represents a linear or branched alkylene or hydroxyalkylene group comprising about 1 to 6 carbon atoms;

  water-soluble salts of (N-alkyl) sulfosuccinic acid

Nates of general formula:

R 'O

i 2

R 1 N CH CH C

503 X R 2

  wherein R 1, R 2, R '2 and X are as previously defined;

  the water-soluble salts of alkylbenzoyl-sulfopro-

  alkyl pionates having the formula: o O O -H

C 1C CH CH CH -C

503 X O R 2

  wherein R 1, R 2 and X are as previously defined; the water-soluble alkyl amide sulfonates designated by the formula:

O / R "2

R CH C N

503 X R'2

  o R 1, R 'and X have been previously defined, R "2 has the same meaning

  that R'2; R'2 and R "2 being identical or different, the water-soluble salts of sulphonates or sulphates of fatty acid esters respectively defined by the formulas:

O O

  And R 1, R '3 and X are as defined in the preceding paragraphs; the sulphonated alkyl ethers corresponding to the formula:

R 1 O R 'SO X

1 3 3

  o R 1, R'3 and X are as previously described;

  N- (alkyl) alkylaryl sulphonates or sulphonates

  water-soluble namides of general formulas:

R 1 SO 2 NH-R OSO 3 X

1 \ / 2 3 3

R 1 O 2 NH R'3 503 X

  R 1, R '3 and X having the same meaning as above;

and their mixtures.

  It should be noted that the fatty acids involved in the compounds

  detergent formulations of the invention may also play the role of

anionic surfactants.

  The anionic surfactants of the compositions of the invention are neutralized prior to their introduction.

  within or in the said compositions in a conventional manner.

  by at least one neutralization agent, chosen imperatively

  alkanolamines and C 2 -C 8 alkaneamines.

  in a significant amount (for example greater than 1% by weight) of another type of neutralizing agent alkali hydroxide, ammonia, is excluded; its effect on the force

  medium ionic being detrimental to the stability of the composi-

tion.

  In particular, mono-, di-, triethanol-

  amines; mono-, di-, triisopropanolamines; 2-amino-2-

  methylpropan-1-ol, tris (hydroxymethyl) aminomethane, 2-amino-

  2-ethyl-1,3-propanediol, and mixtures thereof The use of 2-

  amino-2-methylpropan-1-ol (AMP) or amino-ethyl-propanediol

  (AEPD) is particularly preferred.

  As nonionic surfactants, it is possible to use the agents known to fulfill this function in the liquid liquors of the prior art and in particular: polyalkylene ethers of alkyl, alkylaryl or alkenyl having from 10 to 18 atoms carbon in the alkyl or alkenyl groups and 0 to 12 moles of alkylene oxide Lene (preferably ethylene or propylene);

  esters of sucrose or mono or poly-

  glycosides (1 to 6 glycosides) of fatty acids, optionally ethoxy Lés (3 to 12 moles of ethylene oxide), the fatty chain of which comprises from 8 to 22 carbon atoms; ethoxyalkylamides of formula: (CH 2 CH 2 O) r H

R 1 C N

  o (CH 2 CH 2 O) s H o R 1 is as defined above in the section on anionic surfactants and r and S are integers ranging from 0 to 15 and such that r + S <1;

and their mixtures.

  Anionic and nonionic surfactants provide some degree of performance in the removal of

  stains, of a greasy nature in particular.

  Fatty acids, which are found in the form of soaps

  in the finished product, play the role of surfactants and

  can sequester Ca, Mg cations that

  They also participate in the compositions of the invention.

  Removal of stains of a protein nature.

  at 40% by weight of fatty acids are necessary to obtain good results on said spots Among these fatty acids, unsaturated fatty acids must be found -the detergent compositions of the invention contain from 6 to 10% by weight of said unsaturated fatty acids that are necessary to achieve certain performance, especially on greasy stains, and to achieve the physical stability over time of the compositions of the invention. Saturated fatty acids are advantageously used.

  having from 8 to 22, and preferably 12 to 14, carbon atoms.

  They can be obtained from natural sources such as, for example, vegetable or animal triglycerides (for example, coconut (or coconut) oil, palm oil, palm kernel oil, tall oil, castor oil, tallow, fish oils, fats and mixtures thereof) or can be prepared by synthesis (for example by oxidation of petroleum derivatives or by hydrogenation of carbon monoxide according to

Fisher-Tropsch process).

  As examples of saturated fatty acids that may be used in the compositions of the invention, mention may be made of capric, lauric, myristic, palmitic and stearic acids,

arachidic and behenic.

  Unsaturated fatty acids comprising from 12 to 22 carbon atoms are advantageously used. Monounsaturated fatty acids, and particularly oleic acid, are preferred as examples of unsaturated fatty acids that may be used in the compositions of the invention. in addition to said oleic acid, mention may be made of palmitoleic, linoleic, ricinoleic and linolenic acids. Said fatty acids are neutralized -before their introduction into the compositions of the invention or within

  of these in a conventional way, by at least one neutering agent.

  The neutralization, as for that of the anionic surfactants, excludes the use of a significant amount (greater than 1% by weight) of any other type of surfactant. neutralization The neutralization agents listed in the paragraph relating to said anionic surfactants

  are ideally suited for the neutralization of fatty acids.

  Advantageously, the precursor (s) is used beforehand or in situ

  same agent (s) of neutralization for said fatty acids and

  so-called anionic surfactants.

  Preferably, 2-amino-2-methyl-

  propan-1-ol (AMP) or amino-ethyl-propane-diol (AEPD).

  The sequestering agents of the compositions of the invention are, as indicated above, specific simple or mixed salts of the polyphosphonate type. These are advantageously the salts of the polyphosphonic acids listed below: 1-hydroxyethane acid 1,1diphosphonic acid: HEDP amino tri (methylene phosphonic acid): ATMP ethylene diamino tetra (methylene phosphonic acid): EDTMP

  Hexamethylene diamino tetra (methylenephosphoric acid)

nique): HMDTMP

  Diethylene triamino penta acid (methylene phospho-

  DTPMP These specific salts have been selected for their

  solubility in the compositions of the invention.

  These are simple salts of potassium, ammonium, an alkanolamine or a C 2 -C 8 alkaneamine (salts of

  alkaline cations such as sodium and lithium whose clutter

  ionic concentration is lower than that of potassium are expressly excluded); or mixed salts: an alkali metal (Li, Na, K,), ammonium, an alkanolamine or an alkaneamine

  C 2 -C 8 and an alkaline earth metal (Be, Ca, Mg,).

  Single or mixed salts of HEDP are particularly

favorite.

  Sodium salt of HEDP -sel simple, expressly

  excluded is insoluble in the compositions of the invention.

  Moreover, it proved impossible to obtain

  from it mixed salts, soluble in said composites

  tions. Said mixed salts (Na + / alkaline-earth metal) of HEDP are therefore implicitly excluded mixed salts intervening (in significant amount), possibly mixed, in the

compositions of the invention.

  On the other hand, the use of mixed salts K + / metal

  alkaline earth of HEDP is particularly preferred.

  It is recommended, according to the invention, the intervention of salt (s) of at least two different polyphosphonic acids, and more specifically the joint intervention of at least one salt of HEDP

  and at least one salt of another polyphosphonic acid.

  Indeed, we have demonstrated the existence of a

  synergy on washing performance.

  For example, it has been highlighted that the use of

  In a composition of the invention, a combination of DTPMP / HEDP 0.5% by weight, expressed as active acid of DTPMP, 0.75% by weight, expressed as active acid of HEDP has washing performance higher than of 1.25% or even 2% by weight, expressed as active acid of HEDP alone and also greater than those of 1.25% or even 2% by weight, expressed as the active acid of

DTPMP alone.

  In general, an interesting synergy is observed when the ratio salt (s) of HEDP / salt (s) of HEDP + polyphosphonate salt (s) other (s) than the HEDP (expressed in acid active)

is greater than or equal to 10%.

  Synergy is optimal when the ratio of HEDP salt (s) to polyphosphonate salt (s) other than HEDP (expressed as acid

active) is close to 1.5.

  Mixed salts are obtained from polyphosphoric acid

  known alkali metal, ammonium, alkanolamine or C 2 -C 8 alkaneamine salts by cold mixing with at least one alkaline earth metal salt, such as, for example, magnesium chloride, calcium chlorides, sulphates, formates or

  calcium or magnesium acetates.

  The salts are advantageously mixed before their incorporation.

  poration in the detergent bases, in the form of highly concentrated aqueous solutions The mixing of said solutions generates a homogeneous, transparent liquid, perfectly soluble in said

detergent bases.

  The amount of alkaline earth metal salt to be used optionally for pretreatment of the polyphosphonates obviously depends on the amount of polyphosphonates. For 1 g of polyphosphonate (s) (expressed as active U acid), it is generally from 0.01 to 0.1 g of salt

  (advantageously from 0.015 g to 0.05 g of salt).

  It can be used, generally, from 0.015 to 0.3%

  by weight of alkaline earth salt in the compositions of the invention.

  In any event, sufficient salt should be used to achieve the desired result of dissolving the sequestering agent in the detergent base without saturating said sequestering agent which would no longer be able to perform its function. By using the ingredients specified above, in the amounts indicated, it is therefore possible to prepare concentrated, stable, homogeneous liquid detergent compositions.

and effective.

  By "homogeneous" compositions is meant transparent or slightly opalescent compositions whose total phase stability is complete even after prolonged storage (at least one month) at temperatures of between 20 ° C. and 30 ° C. and at atmospheric pressure. Said compositions may contain, in addition,

  other ingredients such as enzyme (s), anti-inflammatory agent (s)

  redeposition, dye (s), opacifying agent (s), anti-inflammatory agent (s)

  foam, optical brightener (s), perfume (s)

  An organic solvent may also be involved.

  Enzymes, when present, are usually

  0.2 to 5% by weight are chosen from protease, amylase, lipase, cellulase and glucose oxidase enzymes. The intervention of proteases is always beneficial

  may in particular choose said proteases from those

  under the names: Esperase 8 OL (d (NOVO), Savinase

  16 O LDX (NOVO), Savinase 16 O L (NOVO), Maxacal L 300 (GIST-

  BROCCADES), Alcalase 2 LMI (NOVO), Maxatase LS 4000 Q (GIST-

  BROCADES), Maxatase XL 550 (GIST-BROCADES), Durazym 6 O L.

(NOVO).

  Advantageously, the detergent compositions of the invention

  contain at least one protease, in combination with

less an o-amylase.

  Said α-amylase is advantageously chosen from the enzymes marketed under the name Termamyl 300 Lui,

  Maxamyl WL 7,000 respectively by the companies NOVO and GIST-

BROCADES.

  Preferably, the detergent compositions of the invention contain: 0.5 to 5% by weight of proteases, and

0 to 1% by weight of X-amylase.

  Said enzymes intervene mainly on

  The removal of proteinaceous stains.

  Their incorporation into the concentrated detergents of the invention must not adversely affect the stability, the homogeneity of these. Consequently, said enzymes are advantageously pretreated before their incorporation. Their pretreatment is of the type already described for the preparation of salts. mixed polyphosphonates (sequestering agents): it is advisable to mix them cold with at least one salt of alkaline-earth metal dissolved in a minimum of water Advantageously, one carries out a single

  premix enzyme (s) / polyphosphonate (s) / alkali metal salt (s)

earth.

  The enzyme enzyme (s) / salt (s) of metal has alkaline earth

  can also be done within the composition.

  The total amount of alkaline earth metal salt involved in the compositions of the invention does not exceed the maximum defined above: 0.3% by weight of the total weight of

said composition.

  However, it will be noted that said pretreatment of the enzymes, if it is advantageous, is not mandatory. Indeed, the neutralization agents present in the washing base allow, in

  any event, the incorporation of enzyme (s) not pretreated (s).

  The different ingredients of the detergent compositions of the invention are therefore in solution in a minimum of water: not

more than 10% by weight.

  To adjust the viscosity of said compositions and

  To improve their physical stability, these ingredients are advantageously diluted in an organic solvent or a mixture of organic solvents. According to one preferred variant, the detergent compositions of the invention therefore contain from 2 to 20% by weight of organic solvent (s). (s) This level of solvent is advantageously adapted to the mode of use of the detergent composition If it is intended to use it in water-soluble dose sachets, it will obviously be ensured that said solvent level is compatible tible with said sachets-doses Advantageously, this rate of

solvent is less than 15%.

  Said organic solvent is chosen from ethanol, propanol, isopropanol, butanol and glycols (propane

  1,2-diol; propane 1,3-diol; hexylene glycol; the monopropy

  glycol), glycol ethers (ethyl diglycol, butyl-

  glycol), benzyl alcohol and mixtures thereof.

The detergent compositions of the invention are prepa-

  by mixing their ingredients, possibly pretreated.

  The invention will now be described in more detail

  in the following examples, given for illustrative purposes.

Examples 1 to 5

  Five detergent compositions were prepared according to the invention.

tion.

  Their weight composition is given in the table below.

  after. Ingredients Compositions (% by weight) O O O

12 15 10 15

22 20 20

28

27 25 27 25 27

6 8 9 12 9

3 5

13.4, 2

0.5 0.5 _

0.5 0.5

5

8.5 14.2, 8, 0

_ 0.3

0.5

0.1 0.1

0.1 0.1

0.3 0.3

  Alkyl benzene sulfonic acid (Dobanicq 13 (Shell)) 7 fatty acids C 13-C 15 oxyethylenated 7 times C 13-C 15 fatty alcohol oxyethylenated 3 times coconut palm fatty acid bi-distilled oleic acid i HEDP K salt (25% aqueous solution) Na salt of DTPMP (25% aqueous solution) HEDP TEA salt (70% aqueous solution) Triethanolamine Monoethanolamine 2-amino-2-methylpropanol Savinase 8 0 L (NOVO) Maxatase LS 400

(GIST-BROCADES)

  Alcalase 2 5L (NOVO) Termamyl 300L (NOVO) Maxamyl WL 7000

(GIST-BROCADES)

  Magnesium Chloride (50% aqueous solution) Calcium Chloride (50% aqueous solution) Optical Brightener 0.3 0.3 0.3 (continued) Ingredients Compositions (weight%) ethanol-propane-1,2-diol qsp qsp

% 100%

  isopropanol qsp _% ethanol hexylene glycol qsp qsp hi 100% 100% i

  In the five compositions, the phosphorus concentration

  nate expressed as active acid is about 1.2%.

  These five compositions proved stable and perform-

mantes on any type of stains.

  It has furthermore been noted that the composition Q is more efficient than the compositions Q, Q and G especially for the removal of bleachable stains (tea, coffee, wine, blueberry juice). The stated synergy (sequestering agent: salt of HEDP + salt

  another polyphosphonic acid) is confirmed.

  Description of the preparation process

  The compositions of the invention are prepared by simple

mixed.

Advantageously:

  a premix is prepared: enzyme (s) / polyphosphoric acid

  nate (s) / alkaline earth metal salt (optionally); said premix is then added to the mixture constituted by successive incorporation within it of the nonionic surfactant (s), the solvent (s), the

  neutralizing agent (s), fatty acids, or surfactant (s)

  anionic active agent (s) Examples 6 to 11

  These examples are given for comparison.

Example 6

  The composition is distinguished from the composition Q only by the level of oleic acid It is, within it equal

at 5% by weight.

  Said composition G has a physical instability.

Example 7

  The composition Q is distinguished from the composition Q only by the absence of calcium The polyphosphonate does not intervene in the form of a mixed salt Enzymes are not no

more processed.

  The liquid formula obtained is not stable.

Example 8

  The composition is distinguished from the composition only by the intervention of the sodium salt of HEDP instead of its potassium salt. It has been seen that from said sodium salt it is

  impossible to prepare a mixed salt.

  The presence of this sodium salt leads to a physical instability of the composition Q.

Example 9

  The composition is distinguished from the composition s only by the level of saturated fatty acids: 15% Said composition

  Q has deficiencies on enzymatic soils.

Example 10

  Compositions "identical" to the compositions e, Q and Q, respectively, but without oleic acid were prepared.

  compositions have deficiencies on greasy stains.

Example 11

  Compositions "identical" to compositions Q, and O, respectively, but without anionic surfactant (alkyl benzene sulfonic acid) were prepared. These compositions have deficiencies on all the stains (greasy, oxidizable,

enzymatic, particulate).

  The washing performance was highlighted at

test course.

  The compositions are used as a detergent, at a constant dose of 60 g in a cycle without pre-washing in a washing machine of the MIELE W 759 type whose load of 4 kg is constituted

  of cotton items and some pieces of acrylic fabric.

  The washing temperature is 40 C, in a water of 28 H hardness. Realistic tests have been carried out (washing quality notation by several people) and tests by reading.

  optical using an ELREPHO-type reflectometer.

  The course of the said realistic tests is summarized below. A certain number of spots are applied to different strips of fabric (100% white cotton, 50/50 polyester / cotton) which is cut in half in the middle. Each half-band is then washed, one with the product of the invention to be tested,

  the other with the reference product.

  After drying, the half-strips are brought together and

  evaluation is carried out by a panel of several judges.

  With regard to the optical reading tests, they are used to evaluate the washing performance on control tissues (in particular cotton) with artificial stains

  (fat, blood, cocoa, wine,) perfectly homogeneous.

  The appreciation is done by optical reading The reflectometer measures

  the percentage of stain removal compared to the control tissue.

  Detergent compositions having the composition of the composition G 3 above, have also been developed, while varying the nature and the amount of intervention (% weight L in the composition) of the salt (Ca C 12, Mg C 12 , Mg 504, NaCl, Ca

formate).

  The stability over time of these composites has been studied.

tions.

  The results of this study are shown in the table below.

after:

STABILITY

SALT %

  Immediate After 1 day After 3 days 0.00 Ca C 120.10 0.30 0.50 0.00 0.10 Mg C 12 0.10 0.30 0.50 0.00 Mg 50 0.10 g 54 0 , 30 0.50 Limpid Disorder Limpid Limpid Trouble Limpid Limpid Limpid Trouble Limpid Limpid Limpid Trouble Limpid Light Disorder / Precipitated Troub Le / Precipitate Trouble Limpid Light Disorder / Precipitated Trouble / Precipitated Trouble Limpid Light Disorder / Precipitated Trouble / Precipitated Trouble Limpid Light Disorder / Precipitated Trouble / Precipitated Trouble Limpid Light Disturbed / Precipitated Trouble / Precipitated Trouble Limpid Light Disturbed / Precipitated Trouble / Precipitated O "\ j Co (continued)

STABILITY

SALT %

  Immediate After 1 day After 3 days 0.00 Trouble Trouble Trouble Na CL 0.10 Trouble Limpid Trouble / Precipitated 0.30 Trouble Troub Le / Precipitated Heterogeneous 0.50 Trouble Trouble / Precipitated Heterogeneous 0.00 Trouble Trouble Trouble Ca formate 0, Limpid Limpide Limpide 0.30 Trouble Trouble Trouble 0.50 Trouble Trouble Trouble The results given in the table show that +++ salts of Ca ++ and Mg soluble in the composition at 0.10% by weight bring, surprisingly and irrespective of the counter-ion (mineral or organic), a stabilizing effect on the composition and

  prevent the formation of a ladle or precipitate at a concentration

  non-zero, but less than 0.50% of the composition,

  less than 0.1 g of alkaline earth metal salt per g of poly-

  phosphonate expressed as active acid with an optimum around

0.6 g / g of polyphosphonate.

Claims (9)

  A stabile and homogeneous concentrated liquid detergent composition for washing laundry, with a low water content, characterized in that it contains: at 20% by weight (expressed as active acid) of at least one anionic surfactant, preferably 15 to 20% by weight, 40% by weight of at least one nonionic surfactant, 30 to 40% by weight (expressed as active acid) of saturated and unsaturated fatty acids, (s) said unsaturated fatty acid (s) being present in a proportion of 6 to 10% by weight of the total composition, 0.5 to 6% by weight (expressed as active acid) of at least one sequestering agent of the po lyphosphonate type, in the form of a single salt of potassium, ammonium, a C 2 -C 8 alkanolamine or a C 2 -C 8 alkaneamine; or   + mixed alkali metal, ammonium, alkanol   a C 2 -C 8 mine or a C 2 -C 8 alkaneamine on the one hand, and an alkaline earth metal on the other hand; said anionic surfactant (s) and fatty acids having been previously neutralized or neutralized in situ by at least one neutralizing agent chosen from alkanolamines; and alkaneamines, C 2 -C 8.   2 detergent composition according to claim 1, characterized in that the sequestering agent of the type po Lyphosphonate   is selected from the salts of 1-hydroxy-1,1-ethane diphos-   phonic acid (HEDP), amino tri (methyl) phosphonic acid (ATMP), ethylenediamino tetra (methylenephosphonic acid) (EDTMP), hexamethylenedene diamino tetra (methyl) phosphonic acid) ( HMDTMP), diethylenes triamine penta (methyl) phosphenic acid) (DTPMP) and their mixtures.   Detergent composition according to one of claims 1   or 2, characterized in that the sequestering agent is at least one salt of 1-hydroxy-ethane-1,1-diphosphonic acid (HEDP), in   mixing with at least one salt of another phosphonic acid.   4 A detergent composition according to any one of the   Claims 1 to 3, characterized in that the sequestering agent is a mixture of polyphosphonic acid salts containing at least 10% by weight (expressed as active acid) of 1-hydroxy acid salt (s). 1,1-diphosphonic ethane (HEDP).   Detergent composition according to any one of   Claims 1 to 4, characterized in that the mixed salt (s)   of the sequestering agent (s) intervening is (are) obtained by cold mixing at least one salt of an alkali metal, ammonium, a C 2 -C alkanolamine 8 or an alkaneamine C 2 -C 8 acid   polyphosphonic material with at least one salt of an alkaline earth metal.   6. Detergent composition according to claim 5, characterized in that 0.01 to 0.1 g of alkaline earth metal salt (s) are mixed per g of polyphosphonate (s) (expressed as active acid).   Detergent composition according to any one of   Claims 1 to 6, characterized in that the said agent (s)   Anionic surfactant (s) and fatty acids were neutralized with 2-amino-2-methyl propan-1-ol (AMP) or with amino ethyl propane diol (AEPD). Detergent composition according to any one of   Claims 1 to 7, characterized in that it contains 0.2 to 5% by weight of enzymes.   Detergent composition according to claim 8,   characterized in that it contains at least one protease, preferably   in combination with at least one x-amylase.   Detergent composition according to any one of   Claims 1 to 9, characterized in that it contains a   an organic solvent selected from ethanol, propanol, isopropanol and   butanol, glycols, glycol ethers, benzyl alcohol, lique, and their mixtures.   11 Detergent composition according to any one of   Claims 8 to 10, characterized in that it contains:   at 5% by weight of protease enzymes, at 1% by weight of α-amylase enzymes, at 20% by weight of organic solvent, preferably less than 15% by weight. 0.5 -0 -2