FR2743085A1 - Washing agent for laundry applications - Google Patents

Abstract

Washing agent compositions for laundry applications comprise (per 100 parts weight of their weight as dry weight) 35-70 (preferably 40-60) parts weight sodium silicate as principal detergency builder, and 10-35 (preferably 10-25) parts weight of a non-ionic surfactant as principal surfactant agent. Preferably the non-ionic surfactant is chosen from (i) polyoxyalkylated alkylphenols with 6-12C alkyl group and 5-25 oxyalkylene units; (ii) polyoxyalkylated 8-22C aliphatic alcohols with 1-25 oxyalkylene units; (iii) ethoxylated and/or propoxylated alpha - or beta -pinenes containing 1-30 oxyethylene and/or oxypropylene units; (iv) products obtained by condensation of ethylene oxide or propylene oxide with propylene glycol or ethylene glycol; (v) products obtained by condensation of ethylene oxide or propylene oxide with ethylenediamine; (vi) 10-18C -alkyl-dimethylamine oxides and 8-22C - alkoxyethyldihydroxyethylamine oxides; (vii) amides of 8-20C fatty acids; (viii) ethoxylated fatty acids; (ix) ethoxylated fatty amides; (x) ethoxylated amines; (xi) glycerolamides; (xii) alkoxylated amidoamines containing 1-50 oxyalkylene units; (xiii) alkylpolyglycosides with 4-20C in the alkyl group and an average of 0.5-3 glucose units per mole of alkylpolyglycoside; and (xiv) glucosamides.

Description

DETERGENT COMPOSITION FOR WASHING LAUNDRY CONTAINING A
SODIUM SILICATE AS THE MAIN ADJUVANT OF DETERGENCE
The present invention relates to a laundry detergent composition comprising as main detergency builder a sodium silicate, and as a main surfactant a nonionic surfactant.

 The chemical constitution of sodium alkali metal silicates in particular, their hydration state in solid form or in solution, their method of preparation, have a significant influence on their properties of use, especially in the field of detergency.

Indeed, the structure of alkali metal silicates is changing according to their physical state (anhydrous or hydrated solids, concentrated, semi-concentrated or dilute solutions, very concentrated solutions adsorbed on support ...) and their concentration with respect to water .

They are able to generate, by the double process of dissolution and dilution in water, a large variety of more or less ionized species, structures, sizes, stabilities, very different reactivities. The species generated after dissolution and dilution in water are evolutionary in time; they can be reduced in size (by hydrolysis of large polyanions with appearance of oligomers and monomers) or increase (by condensation with appearance of colloidal form, if the pH decreases for example).

In addition, they are capable of constituting mixed species with surfactants.

All these properties make silicates have extremely varied and diversified properties, which can be used to obtain detergency functions (cleaning, dispersion, adsorption, etc.)
Alkali metal silicates are known and have long been used in laundry detergent compositions, but mainly as add-on additives (co-builders or Zcobuilders), and not as a main builder. generally do not represent more than 15% of the weight of said compositions.

 The surface-active agents present in laundry detergent compositions generally consist of anionic surface-active agents (generally of the order of 5 to 50% by weight of said compositions), optionally with small amounts of surfactants added to them. nonionic actives (generally from 1 to 15% by weight of said compositions).

 The Applicant has found that the use in a laundry detergent composition of high concentration sodium silicate as a main builder associated with a nonionic surfactant as a surfactant principle, achieves particularly high and unexpected performances for the removal of stains, in particular composite hydrophobic stains containing fatty pigments such as carbon black or soot, and vegetable and (or mineral) oils, and whatever the fabric.

 The subject of the present invention is therefore detergent compositions for washing laundry, comprising, for 100 parts of their weight, expressed in seconds: in the order of 35 to 70 parts by weight, preferably in the range of 40 to 60 parts by weight, expressed in dry form, of a sodium silicate as a main detergency builder and of the order of 10 to 35 parts by weight, preferably of the order of 10 to 25 parts by weight, expressed as of at least one nonionic surfactant as the main surfactant.

 The term "main detergency builder" means that the amount, if any, in the detergent composition of another type of builder does not exceed 20 parts by weight, preferably not 15 parts by weight, expressed in seconds, for 100 parts by weight of said detergent composition; preferably said detergent composition is free of polyphosphates and zeolites.

 The expression "main detergent surfactant" means that the amount, if any, within the detergent composition of another type of surfactant (anionic in particular) does not exceed 1 part by weight, preferably not 0, 5 parts by weight, expressed in seconds, per 100 parts by weight of said detergent composition.

Most preferably, said composition is free of anionic surfactant.

 The combination according to the invention, of a silicate and a nonionic surfactant in the proportions mentioned above, will be hereinafter referred to as "silicate / nonionic surfactant system".

 The sodium silicate entering said system may be of any kind and shape.

 It may be a metasilicate as well as a disilicate or any other silicate with a molar ratio Rm = SiO 2 / Na 2 O of about 1 to 4, preferably of the order of 1 to 3.3 .

This may be in the form of a concentrated solution (for example concentrated aqueous solution of sodium disilicate at approximately 45% solids content), an amorphous atomized product (for example amorphous disilicate amorphous at about 80% d dry matter), a crystallized product (for example metasilicate or lamellar disilicate described in
US-A4 664 839), a highly concentrated solution on a support (for example cogranules of sodium carbonate and sodium silicate) or a mixture of these different forms of silicate.

ou

Among the nonionic surfactants present in said non-ionic silicate-active system can be cited
polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated) alkylphenols,
polyoxybutylenes) whose alkyl substituent is C6-Cl2 and containing from 5 to 25
oxyalkylene units; by way of example, mention may be made of TRITON X45, X-114, X
100 or X-102 marketed by Rohm & Haas Cy;
polyoxyalkylenated C 8 -C 22 aliphatic alcohols containing from 1 to 25 units
oxyalkylenes (oxyethylene, oxypropylene); for example, we can mention the
TERGITOL 15-S-9, TERGITOL 24-L-6 NMW marketed by Union Carbide
Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4
marketed by Shell Chemical Cy., KYRO EOB marketed by The Procter
& Gamble Cy;
alkoxylated terpenic hydrocarbons, such as ethoxylated α- or pinenes;
and / or propoxylated, containing from 1 to 30 oxyethylene and / or oxypropylene units;
- the products resulting from the condensation of ethylene oxide or
Propylene with propylene glycol, ethylene glycol, such as PLURONIC
marketed by BASF;
- the products resulting from the condensation of ethylene oxide or
propylene with ethylenediamine, such as TETRONIC marketed by BASF;
amine oxides such as C10-C18 alkyl dimethylamine oxides,
C8-C22 alkoxy oxides ethyl dihydroxy ethyl amines;
- C 8 -C 20 fatty acid amides
- ethoxylated fatty acids
ethoxylated fatty amides
ethoxylated amines
glycerolamides;
alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25, all
especially from 2 to 20 oxyalkylene units (preferably oxyethylene), as
N- (bis (poly (oxy-ethanediyl-1,2) amino-2ethyl) alkylamides or N- (bis (poly (oxy)
1,2-ethanediyl) amino) ethyl) -N '- (poly (oxy-ethanediyl-1,2)) - alkylamides of formulas

or

wherein R represents a C2-C22 alkyl radical, n, m1 zQ g and L
representing integers or decimals between 1 and 50, of
preferably between 1.1 and 25, preferably between 2 and 20, or mixtures thereof
the alkylpolyglycosides which can be obtained by condensation (for example by
acid catalysis) of glucose with primary fatty alcohols (US-A-3,598,865;
A-565647; EP-A-132,043; EP-A-132 046 ...) having a C4 alkyl group
C20, preferably C8-C18, and an average number of glucose units of
the order 0.5 to 3, preferably of the order of 1.1 to 1.8 per mole of alkylpolyglycoside
(APG); we can mention in particular those presenting
a Cg-C14 alkyl group and an average of 1.4 glucose units per mole
a C12-C14 alkyl group and an average of 1.4 glucose units per mole
a Cg-C14 alkyl group and an average of 1.5 glucose units per mole
a C8-C10 alkyl group and an average of 1.6 glucose units per mole
marketed respectively under the names GLUCOPON 600 E,
GLUCOPON 600 CUP, GLUCOPON 650 E, GLUCOPON 225 CSUP #, by
Henkel.

glucosamides and, in general, those used in particular in the field of detergency for washing clothes
The use of said silicate / nonionic surfactant system according to the invention makes it possible to dispense with anionic surfactant or to very considerably reduce the level of this type of surfactant in detergent compositions for laundry.

Preferably, said detergent compositions are free of anionic surfactant.

 The detergent compositions according to the invention may be in the form of a powder or in liquid form.

The powdered or liquid laundry detergent compositions according to the invention may contain, besides said nonionic silver-active silicate system, other usual additives for detergent compositions, such as: detergents other than silicates, in quantities not exceeding those mentioned above, such as
polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates,
hexametaphosphates) of alkali metals, ammonium or alkanolamines
- tetraborates or borate precursors
- alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates)
- cogranulates of hydrated silicates of alkali metals and metal carbonates
alkali (sodium or potassium) rich in silicon atoms in Q2 form or
Q3, described in EP-A-488 868, for detergent powder compositions
crystalline or amorphous aluminosilicates of alkali metals (sodium, potassium)
or ammonium, such as zeolites A, P, X, ...

water-soluble polyphosphonates (ethane 1-hydroxy-1, 1-diphosphonates, salts
methylene diphosphonates, ...)
the water-soluble salts of carboxylic polymers or copolymers such as salts
water-soluble polycarboxylic acids with a molecular mass of around
to 100,000, obtained by polymerization or copolymerization of carboxylic acids
ethylenically unsaturated such as acrylic acid, maleic acid or anhydride,
fumaric acid, itaconic acid, mesaconic acid, citraconic acid, acid
methylenemalonique, and especially polyacrylates mass
molecular weight of about 2,000 to 10,000 (US-A-3,308,067), the acid copolymers
acrylic acid and maleic anhydride with a molecular mass of about
75000 (EP-A-66 915)
polycarboxylate ethers (oxydisuccinic acid and its salts, tartrate
monosuccinic acid and its salts, disuccinic acid tartrate and its salts
the hydroxypelycarboxylate ethers
- citric acid and its salts, Mellitic acid, succinic acid and their salts
salts of polyacetic acids (ethyenediaminetetraacetates, nitrilotriacetates, N
(2 hydroxyethyl) nitrilodiacetates)
- C5-C20 alkyl succinic acids and their salts (2-dodecenylsuccinates, lauryl
succinates, ...)
polyacetal carboxylic esters
polyaspartic acid, polyglutamic acid and their salts
polyimides derived from the polycondensation of aspartic acid and / or acid
glutamic
polycarboxymethyl derivatives of glutamic acid [such as N, N
bis (carboxymethyl) glutamic acid and its salts, in particular sodium] or other
amino acids
aminophosphonates such as nitrilotris (methylene phosphonates)
polyfunctional aromatic compounds such as the dihydroxydisobenzenes of anionic surfactants, in amounts not exceeding those mentioned above, such as
the alkyl ester sulfonates of formula R-CH (SO 3 M) -COOR ', where R represents a
C8-C20 alkyl, preferably C10-C16 alkyl, R 'is C1-C6 alkyl,
preferably C1-C3 and M an alkaline cation (sodium, potassium, lithium),
substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-,
tetramethylammonium, dimethylpiperidinium, ...) or an alkanolamine derivative
(monoethanolamine, diethanolamine, triethanolamine, ...);
alkyl sulphates of formula ROSO 3 M, where R represents an alkyl radical or
C10-C24 hydroxyalkyl, preferably C12-C20, and most preferably
C12-C18, M representing a hydrogen atom or a cation of the same definition
above, as well as their ethoxylenated (EO) and / or propoxylenated (OP) derivatives,
with an average of 0.5 to 6 units, preferably 0.5 to 3 EO and / or
OP;
the alkylamide sulphates of formula RCONHR'OSO3M where R represents a radical
C2-C22 alkyl, preferably C6-C20, R 'is C2-C3 alkyl, M
representing a hydrogen atom or a cation of the same definition as above,
as well as their ethoxylenated (EO) and / or propoxylenated (OP)
average of 0.5 to 60 EO and / or OP units;
the saturated or unsaturated C8-C24, preferably C14-C20 fatty acid salts,
C8-C20 alkylbenzenesulfonates, primary or secondary alkylsulfonates
Cg-C221 alkylglycerol sulfonates, sulfonated polycarboxylic acids
described in GB-A-1 082 179, paraffin sulfonates, N-acyl N
alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates,
alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyls
sarcosinates, alkylglycoside sulfates, polyethoxycarboxylates, cation
having the same definition as above.

antifouling agents, in amounts of the order of 0.01-10%, preferably of order
from 0.1 to 5%, and especially of the order of 0.2-3% by weight, agents such as
cellulosic derivatives such as cellulose hydroxyethers, methylcellulose,
Ethylcellulose, hydroxypropyl methylcellulose. rhydroxybutyl methylcellulose
polyvinyl esters grafted on polyalkylene trunks such as
polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048)
polyvinyl alcohols
polyesters based on ethylene terephthalate and / or propylene units
terephthalate and polyoxyethylene terephthalate, with a molar ratio (number of
patterns) ethylene terephthalate and / or propylene terephthalate / (number of units)
polyoxyethylene terephthalate of the order of 1/10 to 10/1, preferably of the order of
111 to 9/1, polyoxyethylene terephthalates having polyoxyethylene units
having a molecular weight of from 300 to 5000, preferably from
600 to 5000 (US-A-3,959,230, US-A-3,893,929, US-A-4,116,896, US-A-4,702,857, US Pat.
US-A-4,770,666);
the sulphonated polyester oligomers obtained by sulphonation of a derived oligomer
ethoxylated allyl alcohol, dimethylterephthalate and 1,2-propylene diol,
having 1 to 4 sulfonated groups (US-A-4,968,451)
the polyester copolymers based on propylene terephthalate units and
polyoxyethylene terephthalate and terminated with ethyl, methyl units (US-A-4
711,730) or polyester oligomers terminated with alkylpolyethoxy groups
(US-A-4,702,857) or sulfopolyethoxy anionic groups (US-A-4,721,580),
sulfoaroyles (US-A4 877 896)
sulphonated polyesters with a number of molecular masses of less than 20 000,
obtained from a diester of terephthalic acid, an acid diester
sulfoisophthalic acid and a diol (FR-A-2720400)
polyesters-polyurethanes obtained by reaction of a mass polyester
Molecular number 300-4000 obtained from adipic acid and / or acid
tereptalic acid and / or sulfoisophthalic acid and a diol on a prepolymer with
terminal isocyanate groups obtained from a polyoxyethylene glycol of
molecular mass of 600-4000 and a diisocyanate (FR-A-2,334,698) anbredépositlon agents, in amounts of about 0.01-10% by weight for a
detergent powder composition, of about 0.01-5% by weight for a composition
liquid detergent, agents such as
ethoxylated monoamines or polyamines, polymers of ethoxylated amines
(US-A-4 597 898, EP-A-1 984)
- carboxymethylcellulose
the sulphonated polyester oligomers obtained by condensation of the acid
isophthalic, methyl and diethylene glycol sulfosuccinate
(FR-A-2,236,926)
the polyvinylpyrollidones of the bleaching agents (reserved for powdered detergent compositions) in amounts of about 0.1-20%, preferably 1-10% by weight of said powdered detergent composition, such as
perborates, such as sodium perborate monohydrate or tetrahydrate
peroxygen compounds such as sodium carbonate peroxyhydrate,
pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide,
sodium persulfate
- percarboxylic acids and their salts (called "percarbonates") such as
magnesium monoperoxyphthalate hexahydrate, metachloroperbenzoate
magnesium, 4nonylaminoXoxoperoxybutyric acid, Fast SnonylaminoR
oxoperoxycaproic acid, diperoxydodecanedioic acid, nonylamide acid
peroxysuccinic acid, decyldiperoxysuccinic acid.

preferably associated with a bleach activator generating in situ in the medium
detergent, a carboxylic peroxyacid; among these activators, we can mention,
tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl
glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose,
Octaacetyl lactose, ...

fluorescers, in an amount of about 0.05-1.2% by weight, agents such as
derivatives of stilbene, pyrazoline, coumarin, fumaric acid, cinnamic acid,
azoles, methinecyanines, thiophenes,. ("The production and application of
fluorescent brightening agents - M. Zahradnik, published by John Wiley & Sons, New
York-1 982-) suds suppressing agents, in amounts of up to 5% by weight,
agents such as
- C1-C24 monocarboxylic fatty acids or their alkaline salts, of ammonium
or alkanolamines, triglycerides of fatty acids
- saturated or unsaturated aliphatic, alicyclic, aromatic or
heterocyclic, such as paraffins, waxes
N-alkylaminotnazines
- monostearylphosphates, monostearyl alcohol phosphates
polyorganosiloxane oils or resins optionally combined with
silica particles of the softening agents, in amounts of about 0.5-10% by weight, agents such as
clays of the enzymes in an amount of up to 5 mg by weight, preferably of the order
0.05-3 mg of active enzyme / g of detergent composition, enzymes such as
proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139,
US-A4 101 457, US-A4 507 219, US-A-4 261 868) and other additives such as
alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol,
glycerin)
- buffering agents
- perfumes
- pigments
The following examples are given for illustrative purposes.

 The detergency and anti-redeposition power measurements of the silicate / nonionic surfactant system were carried out as follows.

PRINCIPLE
The test simulates a simplified machine wash, using a tergotometer. It consists in washing standard and uniform samples of cloths at 40 ° C., with only the product to be tested.The washing lasts thirty minutes and the detergency is evaluated by measuring the whiteness of the pieces of cloth, before and after washing. With the aid of a colorimeter, unsalted control white fabrics are incorporated, which make it possible to evaluate the redeposition of soils by measuring the reflectances before and after washing.

EQUIPMENT AND EQUIPMENT
Material: - Tergotometer: "US TESTING Co Inc. HOBOKEN NJ Model 7243.

- Glaze to iron fabric samples after washing.

- Color Measuring Device "Dr Lange LUCI 100".

Fabrics
Standard fabrics are manufactured by CFT (Center For Test Materials) or by the company "Test Fabric". They have the following characteristics:
Standard soiled fabrics (soiling) number of pieces per test
- CS-2 CFT cocoa (cocoa) 2
- Dirty cotton CS-1 CFT (blood) 2
- Cotton soil K 10D CFT (mineral oil and sebum) 2
- Poyester sali K 30D CFT (sebum) 2
- Asiatic cotton AS-2 CFT (mineral oil and soot) 2
- EMPA 104 CFT cotton polyester (mineral oil and ink) 2
- Polyester type 54 Test Fabric (mineral oil and soot) 2
- Cotton polyester type 54 Test Fabric (mineral oil and soot) 2
Standard white fabrics - CN 1 cotton white, unsalted, CFT 5 - Cotton PCN 1 cotton, white, unsalted, CFT 5 or, for each test, a total of 26 pieces of fabric.

OPERATIVE MODE
Detergency test
The tergotometer is a device consisting of 4 pots of 2 liters stainless steel on which are fitted agitators that are set at 50 cycles per minute (100 round trips). The pots are placed in a water tank regulated at 40 C.

In each pot, 1 liter of water containing the product to be tested is placed:
When the water is at temperature, the pots are introduced into the thermostatic bath by simultaneously triggering the stirring and a stopwatch.

At the end of washing (30 minutes) the baths are recovered (250 cc) for pH control.

The fabrics are rinsed three times with tap water, then dewatered by hand and individually dried individually between two sheets of absorbent white paper.

The tissues are again put between two sheets of clean absorbent paper, and ironed in the ice at a temperature of 110 C.

Color measurement
Measurements are made with the LUCI 100 "colorimeter before and after washing according to the system" L "," a "," b "(Scale from black to white, green to red, and blue to yellow) to measure the power detergent surfactants tested (increased whiteness of pieces of soiled fabrics).

Calculation of detergency
The value "DE" (detergency) is calculated for each type of fabric by geometric sum of the color differences DL, Da and Db before and after washing on the soiled fabrics:
Is
DE detergency = (DL2 + Da2 + Db2) 112
Antiredeposition
The anti-redeposition properties of the tested products are highlighted by the standard white non-saturated CNI cotton fabrics and PCN1 polyester / cotton fabrics, the color of which is measured before and after washing. Redeposition is the difference in reflectance between the initial white tissue and the washed white tissue in the presence of soiled tissue.

Example 1
The intrinsic value of clean detergency is measured by the above test *
- (a) "LABS", sodium dodecylbenzene sulfonate technical (anionic surfactant marketed by ALDRICH), by adding 0.759 LABS (expressed as dry matter) to 1 liter of water;
(b) with the SYNPERONIC A9 linear C12-C14 alcohol ethoxylated with 9 moles of ethylene oxide (nonionic surfactant marketed by ICI) by addition of 0.75 g of
SYNPERONIC A9 (expressed as dry matter) to 1 liter of water;
(c) atomized amorphous sodium silicate of Rm = 2 (containing 20% water) by addition of 1.759 of silicate (expressed as dry matter) to 1 liter of water; * as well as the value of clean detergency
(d) atomized amorphous sodium silicate system of Rm = 2 / LABS, by adding 1.759 of silicate (expressed as dry matter) and 0.75 g of LABS (expressed as dry matter) to 1 liter of water
- (e) atomized amorphous sodium silicate system of Rm = 2 I SYNPERONIC
A9, by addition of 1.759 of silicate (expressed as dry matter) and 0.759 of
SYNPERIONIC A9 (expressed as dry matter) to 1 liter of water.

The results of these measurements are shown in Table 1.

If we compare the intrinsic detergency values of products (a), (b) and (c), we find that the best product is sodium silicate (c), then the anionic surfactant (a) and finally, the nonionic surfactant (b).

The overall detergency values specific to the coupling of the products show that the systems are superior to the products taken alone, (d) being greater than (a) and (c), and (e) greater than (b) and (c), This is not surprising, but the sodium silicate system I SYNPERONIC A9 (e) is far superior to the silicate system! LABS (d).

Performance recovery rate
This recovery rate is obtained by dividing the detergency value of the system (d) or (e) by the sum of the detergency values of each of the constituents of said system [ie value of (a) + value of (c) or value of (b) + value of (c)], then multiplying by 100.

When the recovery rate is greater than 50, it is said that there is performance additivity, the performance of the association being greater than that of the average of the two isolated components.

When this level is greater than 100, it is said that there is synergy, the performance of the association being greater than that of the total of the two components taken in isolation.

The analysis of the results shows with regard to: - overall detergency, a better additivity of the performance of the non-ionic silica-active system [(e) 81%] compared with that of the silicate / anionic surfactant system [(d) 59%].

- detergency by soiling, a very strong synergy of the silicate / nonionic surfactant system (e) for a type of soiling (more than 200%), strong for another type of soiling (121%) and a strong additivity for two other soils (at least 80%), while no synergy is found for the anionic silicateltensioactive system (d).

Example 3
Compared with the stiffness of the above detergency test, the inherent intrinsic detergency value
atomized amorphous sodium silicate (atomized Rm2), by adding 1.75 g of silicate (expressed as dry matter) to 1 liter of water
a nonionic surfactant (AMAM 20E) consisting of a 95/5 by weight mixture of N- (bis (1,2-poly (oxy-1,2-ethyl) amino) ethyl) -dodecamide and N- (bis (1,2-poly (oxy-1,2-ethanediyl) amino) ethyl-N '- (poly (oxy-ethanediyl-1,2)) - dodecamide, having an average degree of ethoxylation of 2, by adding 0.75 g of said mixture (expressed as dry matter) to 1 liter of water
to a nonionic surfactant (AMAM 30E) consisting of a 95/5 by weight mixture of N- (bis (poly (oxy-ethanediyl-1,2) amino-2) ethyl) -dodecamide and N (bis (poly (oxy-ethanediyl-1,2) amino-2) ethyl-N '- (poly (oxy-ethanediyl-12)) -dodecamide, having an average degree of ethoxylation of 3, addition of 0.75 g of said mixture (expressed as dry matter) to 1 liter of water
to a nonionic surfactant (AMAM 70E) consisting of a 95/5 by weight mixture of N- (bis (1,2-poly (oxy-1,2-ethyl) amino) ethyl) -dodecamide and N- (bis (poly (oxy-ethanediyl-1,2) amino-2-ethyl-N'- (poly (oxyethanediyl-1,2)) -dodecamide, having an average degree of ethoxylation of 7, by addition of 0.759 of said mixture (expressed as dry matter) to 1 liter of water at its own accumulated detergency value
to the atomized Rm2 / AMAM 20E system, by adding 1.759 atomized Rm2 and 0.759 AMAM 20E to 1 liter of water.

 to the atomized Rm2 system I AMAM 30E, by adding 1.75 g of atomized Rm2 and 0.759 of AMAM 30E to 1 liter of water.

 to the atomized Rm2 / AMAM 70E system, by adding 1.759 atomized Rm2 and 0.759 AMAM 70E to 1 liter of water.

The results of these measurements are shown in Table 3.

AMAMs 20E, 30E and 70E were prepared as follows: - hydrolysis of hydroxyethyl cocoyl imidazoline
The hydroxyethyl cocoyl imidazoline (1784 g) is hydrolysed in the presence of water (10 wt%) and 86% potassium hydroxide (8.7 g) for 110 minutes at 80 ° C.

- preparation of AMAM 1.20E
The reaction mass is then brought to 100 ° C. and ethylene oxide (325 g) is added over 20 minutes. The product is then left standing at 120 ° C for 30 minutes.

The water is then purged with nitrogen at a temperature of 110 ° C. for 40 minutes and the water content is 0.3% (Karl-Fischer).

Analysis of the reaction medium by liquid chromatography with light scattering evaporative detector shows that the residual amidoamine content is less than 0.1% by weight.

An N - ((bis (2-hydroxyethyl) amino-2-ethyl) -dodecamide / N ((bis (2-hydroxyethyl) amino) ethyl) -N '- (hydroxyethyl-2-dodexamide) mixture is thus obtained according to contents of 95% and 5% respectively and in the form of a pale yellow liquid.

- preparation of AMAM 20E
The AMAM 1.20E obtained as described above is heated to 160 ° C and ethylene oxide (470.6 g) is added over 2 hours, followed by a 30-minute step at 160 ° C. "C. After neutralization of the catalyst with acetic acid, the reaction medium is filtered on absorbing earth (Clarcel DIC).

The average number of ethylene oxide calculated from the ethylene oxide feed is 2.

A mixture of N - ((bis (poly (oxy-ethanediyl-1,2) amino2) ethyl) -dodecamide and
N - ((bis (poly (oxy-ethanediyl-1,2) amino) ethyl) -N '- (poly (oxyethanediyl-1,2)) -dodecamide (average degree of ethoxylation 2) according to weight contents respectively of 95% and 5%.

- preparation of the AMAM 30E
The procedure is similar to the previous one by using 706 g of ethylene oxide (instead of 470.6 g)
A mixture of N - ((bis (1,2-poly (oxy-ethanediyl) amino) ethyl) -dodecarnide and
N - ((bis (poly (oxy-ethanediyl-1,2) amino) ethyl) -N '- (poly (oxy-ethanediyl-1,2)) -dodecamide (average degree of ethoxylation 3) according to weight contents 95% and 5% respectively.

- preparation of AMAM 70E
The procedure is similar to the previous one using 1647 g of ethylene oxide.

A mixture of N - ((bis (poly (oxy-ethanediyl-1,2) amino-2) ethyl) -dodecamide and N - ((bis (poly (oxy-ethanediyl-1,2) amino) ethyl) is obtained) - N '- (poly (oxyethanediyl-1, 2)) - dodecamide (average degree of ethoxylation 7) in weight contents of respectively 95% and 5%.

Example 4
The detergency and anti-redeposition performance of the system
Atomized amorphous sodium silicate of Rm = 2
- SYNPERONIC A9, in a ratio of 35/13 expressed by weight of dry matter, are tested in a washing machine housewife AEG 2050 at 40 C with a tap water of hardness 23H, in a complete detergent formulation whose composition is given in table 4.

The standard soiled fabrics are as follows:
Standard soiled fabrics (soiling) number of pieces per test
- Dirty cotton CS-1 CFT (blood) 2
- Cotton soil K 10D CFT (sebum) 2
- Poyester sali K 30D CFT (sebum) 2
- Asiatic cotton AS-2 CFT (mineral oil and soot) 2
- EMPA 104 CFT cotton polyester (mineral oil and ink) 2
- Polyester Test Fabric (soot) 2
- Polyester Cotton Test Fabric (soot) 2
Standard white fabrics - CN 1 cotton, white, unsalted, CFT 5 - PCN 1 cotton, white, unsalted, CFT 5 or, for each test, a total of 24 pieces of fabric.

In Table 4, the abbreviations have the following meaning perborate Sodium perborate monohydrate
TAED Aqueous solution containing 92% by weight of tetraacetylene
diamine
Carbonate Sodium carbonate
Sulfate Sodium sulphate
SOKALAN CP5fl) BASF acrylic acid / maleic anhydride copolymer
DEQUEST 201 Sodium salt of hydroxyethyldiphosphonic acid
marketed by Monsanto
RHODORSIL 20444Q9 Silicone antifoam from Rhone-Poulenc
The amounts of constituents shown in Table 2 are expressed as weight of active ingredient.

The amount of formulation used is 5 g / liter of water.

These performances are compared to that of an equivalent formulation in which the above system was replaced weight for weight by a temporary system.
Atomized amorphous sodium silicate of Rm = 2
- SYNPERONIC A9,
-LABS in a 35/4/9 ratio expressed by weight of dry matter.

There is a very high level of performance of the compositions of the invention not containing anionic surfactant, and whatever the type of soil and fabric.

Table 1

<tb><SEP> formulation <SEP> (c) <SEP> (a) <SEP> (b) <SEP> (d) <SEP> (e)
<tb> Components
<tb> LABS <SEP> 0.75 <SEP> 0.75
<tb> SYNPERONIC <SEP> A9 <SEP> 0.75 <SEP> 0.75
<tb> Silicate <SEP> 1.75 <SEP> 1.75 <SEP> 1.75
<tb> detergency <SEP> IRP * <SEP> IR
<tb> CS2 <SEP> 14.77 <SEP> 17.39 <SEP> 12.72 <SEP> 15.64 <SEP> 49% <SEP> 11.24 <SEP> 41% <SEP>
<tb> CSi <SEP> 38.23 <SEP> 22.6 <SEP> 5.8 <SEP> 34.98 <SEP> 58% <SEP> 30.11 <SEP> 68%
<tb> K1OD <SEP> 10.22 <SEP> 10.66 <SEP> 12.42 <SEP> 12.48 <SEP> 60% <SEP> 13.02 <SEP> 58%
<tb> K30D <SEP> 21.71 <SEP> 1.62 <SEP> 7.16 <SEP> 20.89 <SEP> 90% <SEP> 13.9 <SEP> 48%
<tb> AS2 <SEP> 7.58 <SEP> 20.76 <SEP> 18.24 <SEP> 14.26 <SEP> 50% <SEP> 23.47 <SEP> 91% <SEP>
<tb> EMPA104 <SEP> 8.7 <SEP> 9.47 <SEP> 9.28 <SEP> 13.37 <SEP> 74% <SEP> 21.79 <SEP> 121% <SEP>
<tb> PE <SEP> 54 <SEP> 2.78 <SEP> 12.77 <SEP> 12.37 <SEP> 2.68 <SEP> 17% <SEP> 34.51 <SEP> 228%
<tb> PEC <SEP> 54 <SEP> 10.87 <SEP> 12.16 <SEP> 17.75 <SEP> 17.89 <SEP> 78% <SEP> 22.8 <SEP> 90%
<tb> Accumulated <SEP> Detergent <SEP> 114.86 <SEP> 107.43 <SEP> 95.74 <SEP> 132.19 <SEP> 59% <SEP> 170.84 <SEP> 81% <SEP >
<tb> Anti-redeposition <SEP>
<tb> CNi <SEP> 6.52 <SEP> 7.54 <SEP> 7.16 <SEP> 6.76 <SEP> 48% <SEP> 6.62 <SEP> 48%
<tb> PCN1 <SEP> 3.77 <SEP> 5.68 <SEP> 3.26 <SEP> 4.53 <SEP> 48% <SEP> 3.05 <SEP> 43%
<tb> * TRP: Performance Recovery Rate
Table 2

<tb><SEP> Formulation <SEP> TPP <SEP> 4A <SEP> Rm2 <SEP> solution <SEP> Rm2 <SEP> atomized
<tb><SEP> 1.75g / l <SEP> 1.75g / l <SEP> 1.75g / l <SEP> 1.75g / l
<tb> DE <SEP> cumulative <SEP> 145 <SEP> 122 <SEP> 118 <SEP> 115
<tb> Formulation <SEP> TPP <SEP> 4A <SEP> Rm2 <SEP> solution <SEP> Rm2 <SEP> atomized
<tb><SEP> 1.75g / l <SEP> 1.75g / l <SEP> 1.75g / l <SEP> 1.75g / l
<tb><SEP> + <SEP> LABS <SEP> 0.75g / l <SEP> + <SEP> LABS <SEP> 0.75g / l <SEP> + <SEP> LABS <SEP> 0.75g / l l <SEP> + <SEP> LABS <SEP> 0.75g / l
<tb> DE <SEP> cumulative <SEP> 230 <SEQ> 186 <SEQ> 161 <SEP> 132
<tb> Formulation <SEP> TPP <SEP> 4A <SEP> Rm2 <SEP> solution <SEP> Rm2 <SEP> atomized
<tb><SEP> 1.75g / l <SEP> 1.75g / l <SEP> 1.75g / l <SEP> 1.75g / l
<tb><SEP> + <SEP> A9 <SEP> 0.75g / l <SEP> + <SEP> A9 <SEP> 0.75g / l <SEP> + <SEP> A9 <SEP> 0.75g / l l <SEP> + <SEP> A9 <SEP> 0.75g / l
<tb> DE <SEP> cumulative <SEP> 205 <SEQ> 165 <SEQ> 177 <SEP> 170
<Tb>
Table 3

<tb> Formulation <SEP> Rm2 <SEP> atomized <SEP> AMAM <SEP> 20E <SEP> Rm2 <SEP> atomized <SEP> 1,75g / l <SEP>
<tb><SEP> 1.75g / l <SEP> 0.75g / l <SEP> + <SEP> AMAM <SEP> 2OE <SEP> 0.75g / l
<tb> DE <SEP> cumulative <SEP> 115 <SEP> 72 <SEP> 152
<tb> Formulation <SEP> Rm2 <SEP> atomized <SEP> AMAM <SEP> 30E <SEP> Rm2 <SEP> atomized <SEP> 1,75g / l <SEP>
<tb><SEP> 1.75g / l <SEP> 0.75g / l <SEP> + <SEP> AMAM <SEP> 3OE <SEP> 0.75g / l
<tb> DE <SEP> cumulative <SEP> 115 <SEP> 84 <SEP> 169
<tb> Formulation <SEP> Rm2 <SEP> atomized <SEP> AMAM <SEP> 70E <SEP> Rm2 <SEP> atomized <SEP> 1,75g / l <SEP>
<tb><SEP> 1.75g / l <SEP> 0.75g / l <SEP> + <SEP> AMAM <SEP> 7OE <SEP> 0.75g / l
<tb> DE <SEP> cumulative <SEP> 115 <SEP> 104 <SEP> 159
<Tb>
Table 4

<tb> Components
<tb> LABS <SEP> 9
<tb> SYNPERONIC <SEP> A9 <SEP> 13 <SEP> 4
<tb> Perborate <SEP> 15 <SEP> 15
<tb> TAED <SEP> 5 <SEP> 5
<tb> Carbonate <SEP> 15 <SEP> 15
<tb> Silicate <SEP> atomized <SEP> Rm2 <SEP> 35 <SEP> 35
<tb> Sulfate <SEP> 9.7 <SEP> 9.7
<tb> SOKALAN <SEP> CP5 <SEP> 5 <SEP> 5
<tb> DEQUEST # <SEP><SEP> 2016 <SEP> 0.2 <SEP> 0.2
<tb> Enzymes <SEP> 0.6 <SEP> 0.6
<tb> RHODORSIL <SEP>#<SEP><SEP> 20448 <SEP> 1.5 <SEP> 1.5
<tb> detergency
<tb> CS1 <SEP> 30.02 <SEP> 23.55
<tb> K10D <SEP> 13.94 <SEP> 8.34
<tb> AS2 <SEP> 13.16 <SEP> 3.41
<tb> EMPA104 <SEP> 19.14 <SEP> 8.83
<tb> PEC <SEP> 21.24 <SEP> 4.72
<tb> K30D <SEP> 8.42 <SEP> 3.09
<tb> PE <SEP> 24.10 <SEP> 3.33
<tb> Cumulative <SEP> Detergence <SEP> 130.02 <SEP> 55.27
<tb> Anti-redeposition
<tb> CN1 <SEP> -2.04 <SEP> -2.66
<tb> PCN1 <SEP> -1.33 <SEQ> -1.62
<Tb>

Claims (7)

 1) Detergent compositions for washing laundry, comprising, for 100 parts of their weight, expressed in seconds, of the order of 35 to 70 parts by weight, preferably of 40 to 60 parts by weight, expressed in the dry state , sodium silicate as a main detergency builder and - on the order of 10 to 35 parts by weight, preferably of the order of 10 to 25 parts by weight, expressed in seconds, of at least one agent nonionic surfactant as the main surfactant.  2) Detergent compositions according to claim 1, characterized in that they contain not more than 20 parts by weight, preferably not more than 15 parts by weight, expressed in seconds, of another type of detergency builder .  3) detergent compositions according to claim 1) or 2), characterized in that they are free of polyphosphates or zeolites.  4) Detergent compositions according to any one of claims 1) to 3), characterized in that they contain not more than 1 part by weight, preferably not more than 0.5 part by weight, expressed in sec, d another type of surfactant.  5) detergent compositions according to any one of claims 1) to 4), characterized in that they are free of anionic surfactant.  6) detergent compositions according to any one of claims 1) to 5), characterized in that the sodium silicate has an SiO 2 / Na 2 O molar ratio of the order of 1 to 4, preferably of the order of 1 to 3.3.  n detergent compositions according to any one of claims 1) to 6), characterized in that the nonionic surfactant is selected from  polyoxyalkylenated alkylphenols whose alkyl substituent is C6Cl2 and  containing from 5 to 25 oxyalkylene units;  polyoxyalkylenated C 8 -C 22 aliphatic alcohols containing from 1 to 25 units  oxyalkylene;  ethoxylated and / or propoxylated α-or pinenes containing from 1 to 30 units  oxyethylene and / or oxypropylene;  - the products resulting from the condensation of ethylene oxide or  propylene with propylene glycol or ethylene glycol;  - the products resulting from the condensation of ethylene oxide or  propylene with ethylenediamine;  the alkyl oxides C 1 -C 18 dimethylamines, the alkoxy oxides C 8 -C 22 ethyl  dihydroxyethylamines;  amides of C8-C20 fatty acids;  ethoxylated fatty acids;  ethoxylated fatty amides;  ethoxylated amines;  glycerolamides;  alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25, all  particularly from 2 to 20 oxyalkylene units;  alkylpolyglycosides having a C 4 -C 20 alkyl group, preferably  C8-C18, as well as an average number of glucose units of the order of 0.5 to 3, of  preferably of the order of 1.1 to 1.8 per mole of alkylpolyglycoside;  - glucosamides.  8) Compositions according to claim 7, characterized in that the surfactant is chosen from N- (bis (poly (oxy-ethanediyl-1,2) amino-2ethyl) alkylamides or N- (bis (poly ( 1,2-oxy-ethanediyl) amino) ethyl) -N '- (poly (oxy-ethanediyl-1,2)) - alkylamides of formulas

 and

 formulas in which R represents a C2-C22 alkyl radical, n, m, p, q and L representing integers or decimals of between 1 and 50, preferably between 1.1 and 25, preferably between 2 and 20, or their mixtures.