EP0592265A1 - Detergent composition containing a polyimide biopolymer hydrolysable in the washing medium - Google Patents

Abstract

The invention relates to a detergent composition containing at least one polyimide biopolymer or one of its derivatives, characterised in that this polymer has a COO<-> charge density greater than 5.10<-4> mol/g and in that it is capable of increasing this COO<-> charge density in the washing bath. The invention is also targeted at the uses of a polyimide biopolymer as defined above in powder detergent compositions.

Description

The subject of the present invention is a detergent composition containing a polyimide biopolymer capable of generating by hydrolysis in a washing medium a polypeptide "builder" at least partially biodegradable and the applications in the field of detergency of said composition.

By "builder" is intended to denote according to the invention, any constituent which improves the performance of surfactants of a detergent composition.

• il assure l'enlèvement des ions indésirables, notamment alcalino-terreux (calcium, magnésium), par séquestration ou précipitation, pour prévenir la précipitation des tensio-actifs anioniques,
• il apporte une réserve d'alcalinité et de force ionique,
• il maintient en suspension les salissures extraites et
• il empêche les incrustations minérales du linge observées en cours de lavage.

In general, the activity of this "builder" in the laundry environment manifests itself in the following aspects:

• it ensures the removal of undesirable ions, in particular alkaline-earth ions (calcium, magnesium), by sequestration or precipitation, to prevent the precipitation of anionic surfactants,
• it provides a reserve of alkalinity and ionic strength,
• it keeps the extracted dirt in suspension and
• it prevents mineral deposits from the linen observed during washing.

For a very long time, tripolyphosphates have been the most frequently used "builders" in detergent compositions and detergents. However, for ecological imperatives, we are now looking for substitutes for them.

As such, zeolites and copolymers of acrylic acid and maleic anhydride have already been proposed.

Unfortunately, zeolites alone cannot replace tripolyphosphates; they must be reinforced in their action by other additives.

As for the copolymers of acrylic acid and maleic anhydride (or their alkali or ammonium salts), intended more particularly for use as incrustation inhibitors (European patent n ° 25.551), they have the disadvantage of not be biodegradable in a natural environment.

Recently, the Applicant has proposed a detergent composition having simultaneously excellent primary and secondary detergency properties and an ability to generate, by hydrolysis in a laundry medium, a "builder" at least partially biodegradable (Patent Application EP 92400875.8 ).

This detergent composition is characterized by the use as a constituent of a polyimide biopolymer having a charge density COO⁻ which can range from 0 to 5 × 10⁻⁴ mole / g of polymer and capable of acquiring in the washing bath a COO⁻ charge density at least equal to 10⁻³ mole / g of polymer.

Today, the present invention relates more particularly to detergent compositions, one of the constituents of which is at least one polyimide biopolymer or one of its derivatives, characterized in that this constituent has a charge density COO⁻ greater than 5. 10⁻ ⁴ mole / g and in that it is capable of increasing this charge density COO⁻ in the detergent bath.

The detergent composition which is the subject of the present invention advantageously leads, by hydrolysis within the washing bath of the polyimide biopolymer, to a builder at least partially biodegradable.

According to a preferred embodiment of the invention, the initial charge density COO⁻ of the polyimide biopolymer or derivative thereof is less than or equal to 2. 10⁻³ mole / g of polymer.

The term “detergent composition” denotes, according to the invention, washing machine detergents, dishwasher detergents or any other washing product for household use.

The term "detergent bath" or "detergent medium" means the aqueous detergent solution (detergent composition) present in the washing machine during the washing cycles; the quantity of detergent present is that recommended by the manufacturer; this is generally less than 20g / liter; the pH of such a solution is greater than or equal to 9.

By way of example of polyimide biopolymers having a charge density COO⁻ in accordance with the present invention and which can be used, mention may be made of polyimides derived from the polycondensation of aminodiacides, in particular aspartic or glutamic acid or precursors of said aminodiacides; these polymers dissolve in water at basic pH with the formation of free COO⁻ functions.

These polymers can be homopolymers derived from aspartic or glutamic acid, as copolymers derived from aspartic acid and glutamic acid in any proportion, or copolymers derived from aspartic acid and / or glutamic and other amino acids (for example up to 15% by weight, preferably less than 5% by weight, other amino acids).

Among the copolymerizable amino acids, there may be mentioned glycine, alanine, valine, leucine, isoleucine, phenylalanine, methionine, tryptophan, histidine, proline, lysine, arginine, serine , threonine, cysteine ...

Said polyimide biopolymers or their derivatives can have a weight-average molecular mass of the order of 300 to 10⁷ and generally of the order of 500 to 60,000.

These, like the polyimides derived from aspartic or glutamic acid, can be prepared in particular by thermocondensation of said amino acid (s) in a substantially anhydrous medium, as described in JACS, 80 , 3361 (1958), J. Med. Chem. 16 , 893 (1973), Polymer 23 , 1237 (1982) or in U.S. Patent No. 3,052,655.

The charge density COO⁻, required according to the invention, can also be satisfied by using partially hydrolyzed polyimide biopolymers. These compounds, also designated by the term polyimide derivatives, are in particular accessible by controlled opening of at least one of the imide rings of a primary polyimide chain with formation of carboxylates.

The amount of polyimide biopolymer entering the detergent composition forming the subject of the invention can range from 0.2 to 80% by weight and preferably from 2 to 5% by weight of said detergent composition.

In addition to the polyimide biopolymer or derivative thereof, there is present, in the detergent composition, a surfactant, in an amount which can range from 2 to 50%, preferably from 6 to 30%, by weight of said detergent composition. .

• les agents tensio-actifs anioniques du type savons et métaux alcalins (sels alcalins d'acides gras en C8 - C24), sulfonates alcalins (alcoylbenzène sulfonates en C₈ -C₁₃, alcoylsulfonates en C₁₂ - C₁₆, alcools gras en C₆ - C₁₆ oxyéthylénés et sulfatés, alkylphénols en C₈ - C₁₃ oxyéthylénés et sulfatés), les sulfosuccinates alcalins (alcoylsulfosuccinates en C₁₂ - C₁₆)...
• les agents tensio-actifs non ioniques du type alcoylphénols en C₆ - C₁₂ polyoxyéthylénés, alcools aliphatiques en C₈ - C₂₂ oxyéthylénés, les copolymères bloc oxyde d'éthylène - oxyde de propylène, les amides carboxyliques éventuellement polyoxyéthylénées,
• les agents tensio-actifs amphotères du type alcoyldiméthylbétaïnes,
• les agents tensio-actifs cationiques du type chlorures ou bromures d'alkyltriméthylammonium, d'alkyldiméthylammonium.

Among the surfactants included in the detergent composition forming the subject of the invention, there may be mentioned:

• anionic surfactants such as soaps and alkali metals (alkali salts of C8 - C24 fatty acids), alkali sulfonates (C₈ -C₁₃ alkylbenzene sulfonates, C₁₂ - C₁₆ alkyl sulfonates, oxyethylenated and sulfated C alcool - C₁₆ fatty alcohols , oxyethylenated and sulfated C₈ - C₈ alkylphenols), alkali sulfosuccinates (C₁₂ - C₁₆ alkyl sulfosuccinates) ...
• non-ionic surfactants of the polyoxyethylenated C₆ - C₁₂ alkylphenols type, oxyethylenated C₈ - C₂₂ aliphatic alcohols, ethylene oxide-propylene oxide block copolymers, optionally polyoxyethylenated carboxylic amides,
• amphoteric surfactants of the alkyl dimethyl betaines type,
• cationic surfactants of the chlorides or bromides of alkyltrimethylammonium, of alkyl dimethylammonium.

Various constituents can also be present in the detergent composition of the invention to lead to detergents or powdered cleaning products.

• des "builders" du type:
  • . phosphates à raison de moins de 25% du poids total de formulation,
  • . zéolithes jusqu'à environ 40% du poids total de formulation,
  • . carbonate de sodium jusqu'à environ 80% du poids total de formulation,
  • . acide nitriloacétique jusqu'à environ 10% du poids total de formulation,
  • . acide citrique, acide tartrique jusqu'à environ 20% du poids total de formulation, la quantité totale de "builder" (polyimide précurseur de builder + autres builders) correspondant à environ 0,2 à 80%, de préférence de 20 à 45% du poids total de ladite composition détergente,
• des inhibiteurs de corrosion tels que les silicates jusqu'à environ 25% poids de total de ladite composition détergente,
• des agents de blanchiment du type perborates, chloroisocyanates, N, N, N', N' - tétraacétyléthylénediamine (TAED) jusqu'à environ 30% du poids total de ladite composition détergente,
• des agents anti-redéposition du type carboxyméthylcellulose, méthylcellulose en quantités pouvant aller jusqu'à environ 5% du poids total de ladite composition détergente,
• des agents anti-incrustation du type copolymères d'acide acrylique et d'anhydre maléïque en quantité pouvant jusqu'à 10% environ du poids total de ladite composition détergente,
• des charges du type sulfate de sodium pour les détergents en poudre en quantité pouvant aller jusqu'à 50% du poids total de ladite composition détergente.

May also be present in the detergent composition described above:

• "builders" like:
  • . phosphates at a rate of less than 25% of the total weight of the formulation,
  • . zeolites up to around 40% of the total formulation weight,
  • . sodium carbonate up to approximately 80% of the total formulation weight,
  • . nitriloacetic acid up to approximately 10% of the total formulation weight,
  • . citric acid, tartaric acid up to approximately 20% of the total formulation weight, the total quantity of "builder" (polyimide precursor of builder + other builders) corresponding to approximately 0.2 to 80%, preferably from 20 to 45% the total weight of said detergent composition,
• corrosion inhibitors such as silicates up to about 25% by weight of the total of said detergent composition,
• bleaching agents of the perborate, chloroisocyanate, N, N, N ', N' - tetraacetylethylenediamine (TAED) type up to approximately 30% of the total weight of said detergent composition,
• anti-redeposition agents of the carboxymethylcellulose, methylcellulose type in amounts which can range up to approximately 5% of the total weight of said detergent composition,
• anti-scaling agents of the acrylic acid and maleic anhydrous copolymer type in an amount which can be up to approximately 10% of the total weight of said detergent composition,
• fillers of the sodium sulfate type for powdered detergents in an amount which can range up to 50% of the total weight of said detergent composition.

The present invention also relates to the uses of a polyimide biopolymer as defined above, in powdered detergent compositions.

The detergent composition which is the subject of the invention has good efficacy, whether in primary detergency or in secondary detergency. In addition, the incorporation of a polyimide which is only hydrolyzable in a detergent medium, guarantees the detergent composition stability, during storage, superior to that of a composition directly containing the biodegradable polypeptide.

The following examples and the single figure are given for information only and cannot be considered as limiting the scope and spirit of the invention.

The single figure represents the variation in the level of a calcium carbonate sedimentate as a function of the polymer concentration.

EXAMPLE 1

Preparation of a low molecular weight polycuccinimide

450g of anhydrous ammonium maleate are spread on a rectangular stainless steel tray without edge on an area of approximately 95 cm². The tray is placed in a THERMOSI SR 2000 ® ventilated oven without air and preheated to 230 ° C. After two hours of reaction, the extractable rate is evaluated at 1.64% w / w. A powder is recovered which is a polysuccinimide (IR spectrometry), whose number average molecular mass Mn is equal to 900 (measurement of viscosity in 0.5 N NaOH).

EXAMPLE 2

Formulation of a washing machine detergent composition from the polysuccinimide of Example 1.

To the powder, prepared in Example 1, various additives are introduced by dry mixing in order to obtain the following detergent composition (detergent): LAUNDRY COMPOSITION % IN WEIGHT Linear alkylbenzene sulfonate 7.5 CEMUSOL LA 90® (polyoxyethylenated lauric acid marketed by SFOS) 4 Zeolite 4 A 24 Na silicate (SiO₂ / Na₂O = 2) 1.5 Na carbonate 10 TAED 2 Na perborate 15 Ethylenediamine tetracetic acid 0.1 Polysuccinimide above prepared 3 Tinopal DMSX® 0.1 Tinopal SOP® (brighteners marketed by CIBA-CEIGY) 0.1 Silicone defoamer 0.2 Alcalaze 0.15 Savinaz (enzymes) 0.15 Na sulfate qs 100%

We will call "control detergent" a detergent of composition above but not containing polysuccinimide.

The performance of this detergent has been tested and is explained in the following examples.

EXAMPLE 3

This example highlights the sequestration capacity of the calcium ions of the polysuccinimide of Example 1 after in situ hydrolysis to polyaspartic acid in basic medium.

The sequestration capacity of calcium ions is measured using an electrode having a selective membrane permeable to calcium ions.

We first draw a calibration curve using 100 ml of a sodium chloride solution at 3 g / l of pH 10.5 to which are added quantities of calcium ions varying from 10⁻⁵ to 3 x 10⁻³ mole / l and draw the potential curve delivered by the electrode as a function of the concentration of free Ca²⁺ ions.

The polysuccinimide of Example 1 is hydrolyzed with a concentrated sodium hydroxide solution until a 20% by weight solution of sodium polyaspartate of pH = 10.5 is obtained. The solution obtained is called "hydrolyzate".

• la constante de complexation des ions calcium, K, du polymère
• le nombre So de sites de complexation du polymère définis par : $$\frac{\text{[Ca²⁺] libre}}{\text{[Ca²⁺] fixé}}\text{=}\frac{\text{1}}{\text{KSo}}\text{+}\frac{\text{1}}{\text{So}}\text{[Ca²⁺] libre}$$
  

This solution is diluted until 100 g of aqueous solution containing 10 g / l of sodium polyaspartate are obtained; the pH is adjusted to 10.5 with a concentrated sodium hydroxide solution. 0.3 g of powdered sodium chloride is added. Calcium ions are also introduced in quantities varying between 10⁻⁵ to 3.10⁻³ moles / l and the straight line [Ca²⁺] free / [Ca²⁺] fixed = f ([Ca²⁺] free) is drawn.
From this line we determine:

• the complexing constant of calcium ions, K, of the polymer
• the number So of complexing sites of the polymer defined by: $$\frac{\text{[Ca²⁺] free}}{\text{[Ca²⁺] fixed}}\text{=}\frac{\text{1}}{\text{KSo}}\text{+}\frac{\text{1}}{\text{So}}\text{[Ca²⁺] free}$$
  

According to this evaluation method, it is found that the polyaspartic acid obtained by hydrolysis of the polysuccinimide of Example 1 has 2.6 x 10⁻³ site / g of polymer whose affinity is Log K = 3.6.

EXAMPLE 4

This example demonstrates the capacity of the polysuccinimide of Example 1 to disperse calcium carbonate, after hydrolysis in situ to aspartic acid in basic medium.

In a 100 cm³ test tube (height 26 cm; diameter 3cm), 2 g of precipitation calcium carbonate are dispersed in 100 ml of an aqueous solution of pH 10.5 (NaOH) containing 3 g / l of NaCl, 3 x 10⁻³ mole / l of CaCl₂ and the hydrolyzate at different concentrations.

The level of the sedimentate in cm³ is measured after 10 minutes and the curve of the sedimentate level is plotted as a function of the concentration in ppm of the polymer (expressed in sec).

The curve of the single figure first shows a flocculation phenomenon (too low coverage rate of the particles by the polymer) then restabilization.

This capacity for stabilizing mineral particles is particularly advantageous since it is known that the latter are the cause of incrustation phenomena due to deposits which accumulate on cotton.

EXAMPLE 5

This example demonstrates the capacity of the polysuccinimide of Example 1 to inhibit the crystallization of calcium carbonate, after hydrolysis in situ to polyaspartic acid in basic medium.

The property of inhibition of crystallization of the calcium carbonate of this product is demonstrated using the method described by Z. AMJAD in LANGMUIR 1987, 3, 224-228.

The measurement is carried out in a closed cell thermostatically controlled using a supersaturated solution containing 10⁻³ mole / l of sodium bicarbonate and 2 x 10⁻³ mole / l of calcium chloride (pH = 8.6) , to which 5 g / l of synthetic calcium carbonate are added (specific surface = 80 m² / g; theoretical diameter = 20 nm); measuring the reduction in the rate of crystallization of the calcium carbonate obtained by adding 500 ppm of the hydrolyzate (expressed as dry) as prepared in Example 3.
The results are as follows:

EXAMPLE 6 Inhibitory effects of incrustation

• . textiles coton Testfabric 405 (4)
• . coton Krefeld 12A (8)

This effect was measured after 20 washes in the absence of soiled fabrics on the following unsoiled test pieces:

• . cotton textiles Testfabric 405 (4)
• . cotton Krefeld 12A (8)

The mineral incrustation is calculated from the ash rate (in% relative to the total weight of the cotton) of the fabrics washed, dried and burnt at 950 ° C for 3 hours.

The encrusting inhibiting effect is appreciated by the ratio of ash rate with additives / ash rate without additives which appears under the letter T in Table I below.

Claims (17)

1) Detergent composition, one of the constituents of which is at least one polyimide biopolymer or one of its derivatives, characterized in that this constituent has a charge density COO⁻ greater than 5. 10⁻⁴ mol / g of polymer and in this that it is likely to increase this density of charge COO⁻ in the detergent bath. 2) Detergent composition according to claim 1 characterized in that said polyimide biopolymer has an initial charge density less than or equal to 2. 10⁻³ mole / g of polymer. 3) Detergent composition according to claim 1 or 2 characterized in that said polyimide biopolymer derives from the polycondensation of aminodiacides or of precursors of said aminodiacides. 4) Detergent composition according to claim 1, 2 or 3 characterized in that said polyimide biopolymer derives from the polycondensation of aspartic acid and / or glutamic acid or the precursors of said acid (s). 5) Detergent composition according to one of claims 1 to 4 characterized in that said polyimide biopolymer is partially hydrolyzed. 6) detergent composition according to any one of claims 1 to 5 characterized in that said polyimide biopolymer has a weight average molecular weight of the order of 300 to 10⁷. 7) Detergent composition according to claim 6 characterized in that said polyimide biopolymer has a weight average molecular weight of the order of 500 to 60,000. 8) Detergent composition according to any one of claims 1 to 7 characterized in that said polyimide biopolymer represents from 0.2 to 80% by weight of said detergent composition. 9) Detergent composition according to claim 8 characterized in that said polyimide biopolymer represents from 2 to 5% by weight of said detergent composition. 10) Detergent composition according to any one of claims 1 to 9 characterized in that a surfactant is present in an amount ranging from 2 to 50% by weight of said composition. 11) Use, in powdered detergent compositions, of a polyimide biopolymer or one of its derivatives, having a charge density COO⁻ greater than 5.10⁻⁴ mole / g of polymer and capable of increasing in a washing medium its charge density COO⁻, as a substance generating in the laundry medium a polypeptide "builder" component at least partially biodegradable. 12) Use according to claim 11 characterized in that said polyimide biopolymer is derived from the polycondensation of aminodiacides or of the precursors of said aminodiacides. 13) Use according to claim 12 or 11 characterized in that said polyimide biopolymer is derived from the polycondensation of aspartic acid and / or glutamic acid or the precursors of said acid (s). 14) Use according to one of claims 11 to 13 characterized in that the polyimide is also partially hydrolyzed. 15) Use according to one of claims 11 to 14 characterized in that said polyimide biopolymer has a weight average molecular weight of the order of 300 to 10⁷. 16) Use according to claim 15 characterized in that said polyimide biopolymer has a weight average molecular weight of the order of 500 to 60,000. 17) Use according to one of claims 11 to 16 characterized in that said polyimide biopolymer is present in an amount ranging from 0.2 to 80% by weight of said detergent powder composition.

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