WO1996012784A1

WO1996012784A1 - Zeolite and phosphate-free detergent builder composition

Info

Publication number: WO1996012784A1
Application number: PCT/FR1995/001378
Authority: WO
Inventors: Daniel Joubert; Pascal Taquet
Original assignee: Rhone-Poulenc Chimie
Priority date: 1994-10-21
Filing date: 1995-10-18
Publication date: 1996-05-02
Also published as: FR2726002B1; AU3808295A; FR2726002A1

Abstract

Detergent builder composition comprising a fully soluble zeolite and phosphate-free builder composition containing cogranulates comprising an alkali metal carbonate; an alkali metal silicate nSiO2-M2O, wherein M is an alkali metal, the SiO2-M2O molar ratio = n being 1.5-3.5; and silicate-bound water, the weight ratio (silicate-bound water)/(dry silicate) being greater than 33:100. The detergent builder composition also comprises an anti-incrustation system comprising a phosphonate or a mixture of organic phosphonates in an amount wherein the weight ratio of phosphate to carbonate is 0.007-0.05. The invention also concerns the use of said detergent builder composition in association with at least one detergent in washing machine detergent compositions, and also these washing compositions.

Description

DETERGENCE ADJUVANT COMPOSITION WITHOUT ZEOLITHS OR PHOSPHATES

The present invention relates to a composition of detergency builder usable for washing machine in a machine comprising a fully soluble builder system without zeolite or mineral phosphates and an anti-encrustation system.

Cotton inlay is a common detergency problem, and the use of formulas with high sodium carbonate contents (whether or not containing zeolites) has led to an increase in this phenomenon. The incrustation is essentially linked to the precipitation and / or the exchange of calcium in the washing water with the adjuvant systems consisting of sodium carbonate and to a lesser degree of sodium silicate and and zeolite. The particles resulting from these reactions are then deposited by electrostatic effect on the cotton. This cumulative phenomenon results in a rough touch of the laundry.

In order to reduce the incrustation, the washing machines employ various systems making it possible to control or inhibit the crystal growth of the precipitates and in particular that of the calcium carbonate. Mention may be made, for the best known, of polymers of the sodium copolymer (acrylate / maleate) type which act essentially as dispersants by adsorbing on the surface of the solid formed in the detergent medium. The surface charge of the particle becomes negative thus preventing deposition on the cotton which is also negatively charged.

These generally polyfunctional systems can intervene in the reduction of incrustation by acting at the same time as inhibitors of crystal growth, as precipitate dispersants and as calcium sequestering agents.

The invention aims to resolve the problems related to calcium encrustation in formulas without zeolites or mineral phosphates and with a high sodium carbonate content.

To this end, the subject of the invention is a detergency builder composition comprising, on the one hand, a fully soluble adjuvant system without zeolite or mineral phosphates, based on cogranules comprising an alkali metal carbonate, a metal silicate alkaline nSi0 ₂ -M ₂ 0, where M represents an alkali metal and the molar ratio Si0 ₂ / M ₂ 0 = n is 1.5 to 3.5, and water associated with the silicate, the weight ratio (water associated with silicate) / (silicate expressed as dry) being greater than 33/100 and, on the other hand, an anti-encrustation system comprising a phosphonate or a mixture of organic phosphonates in an amount such as the weight ratio (phosphonate) / ( carbonate) is from 0.007 to 0.005, preferably from 0.01 to 0.03.

Said co-granules are the subject of European patent applications EP-A-0488 868 and EP-A-0561 656 filed by the Applicant. These products are known for their detergency builder properties and their detergent behavior, which is particularly suitable for washing machine and dishwasher applications.

The co-granules known from EP-A-0488 868 are obtained by adsorption and / or absorption of an aqueous solution of hydrated alkali metal silicate, on a particulate inorganic support chemically inert with respect to the silicate, namely a carbonate of alkali metal. They are characterized in particular by their water content "associated" with silicate. By this expression, we mean the water remaining associated with the silicate after adsorption and / or absorption, that is to say the water of the supported solution which is not combined with the mineral support, in particular in the form of 'crystallized hydrate. The amount of mineral support brought into contact with the silicate solution is adjusted so that the weight ratio (water associated with the silicate) / (silicate expressed as dry) is greater than 33/100. The upper limit of the weight ratio (water remaining associated with the silicate) / (silicate expressed in dry) corresponds to the limits for which a silicate is kept in powder form with fluid flow ("free flowing"), that is to say usable in detergency. To fix the ideas, the weight ratio (water remaining associated with the silicate) / - (silicate expressed as dry) - is advantageously less than or equal to approximately 120/100.

The preparation of the cogranules can be done by any available means of bringing the silicate solution into contact with the carbonate particles.

A method of preparation consists in (a) spraying an aqueous solution based on alkali metal silicate or based on a mixture of silicate and alkali metal carbonate on a moving bed of particles based on alkali metal carbonate or based on the identical silicate-carbonate mixture cited above, traveling in a rotary granulation device, the speed of movement of the particles, the thickness of the moving bed and the flow rate of the sprayed solution being such that each particle is transformed into a plastic cogranulate by coming into contact with other particles, (b) possibly drying said cogranules obtained in (a), these steps being carried out so that the weight ratio (water associated with silicate) / (sili- cate expressed in sec) remains greater than 33/100.

Preferably, between steps (a) and (b), the cogranules are subjected to a densification operation.

Thus, mention may be made, by way of example of agents based on silicate and carbonate such as described above, Nabion ® manufactured and marketed by Rhône-Poulenc.

According to the present invention, the weight ratio of silicate to carbonate in the cogranules is advantageously from 5/95 to 45/55, preferably from 15/85 to 35/65.

Among the alkali metal silicates and carbonates, there may be mentioned in particular those of sodium and potassium, and very particularly those of sodium.

These cogranules are used as tripolyphosphate (TPP) substitutes in detergent compositions; indeed, they provide the dispersing power of TPP thanks to the silicate as well as the alkalinity and a softening effect of the washing water thanks to the carbonate.

However, the level of incrustation of formulas containing these cogranules is higher than that obtained with a conventional formula containing TPP or zeolites.

To overcome this drawback, the detergency builder composition according to the invention contains said anti-encrustation system.

The present inventors have discovered that the incrustation rate is linked to the ratio of the proportions of phosphonate and carbonate present in the detergent composition.

To prevent encrustation in a satisfactory manner, the phosphonate / carbonate ratio is between 0.007 and 0.05, preferably between 0.01 and 0.03.

In addition to the cogranules described above, the detergency builder composition may optionally contain free sodium carbonate, that is to say not associated with a silicate. The carbonate is then present in proportions such that the total phosphonate / carbonate ratio remains within the range indicated above.

The organic phosphonates used in the detergency builder composition according to the invention can in particular be chosen from amino-tris-methylene-phosphonic acid or its pentasodium salt, 1-hydroxy ethylene-1,1-diphosphonic acid or its tetrasodium salt, ethylenediamine tetra (methylphosphonic) or its pentasodium salt, hexapotassium salt of hexamethylenediamine tetra (methylphosphonic) and diethylenetriamine-penta acid (methylphosphonic) or its heptasodium salt.

The dose of phosphonate present in the anti-encrustation system is very low and makes it possible to obtain a detergent composition without phosphate, non-encrusting and which respects the environment.

The anti-encrustation system of the invention can also comprise a compound or a mixture of organic compounds capable of reducing calcium encrustation in the tissue, in particular by virtue of properties inhibiting crystal growth, dispersing precipitates. or calcium sequestration.

These compounds are advantageously chosen from copolymers of acrylic acid and maleic anhydride and the sodium salts derived therefrom, sodium polyacrylates, sodium polyaspartate, polysuccinimide, polyides derived from amino acids and their hydrolysates, N, N-dicarboxymethyl-2-aminopentane- acid

1,5-dioic acid and the salts derived therefrom, and are preferably present in the builder composition in an amount of 2 to 20% by weight.

Among these compounds, N, N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and the salts derived therefrom are very advantageous since they are fully biodegradable and therefore lead to compositions which respect try the environment better.

The above compound (s) act in synergy with the phosphonate (s) to provide even lower incrustation rates. Thus, preferably, the anti-encrustation system comprises a mixture of an organic phosphonate chosen from the tetrasodium salt of 1-hydroxyethylene-1,1-diphosphonic acid and the heptasodium salt of diethylenetriamine-penta acid (methylphosphonic) and an acrylate / sodium maleate copolymer.

An anti-incrus¬ tation system is also preferred which comprises a mixture of an organic phosphonate chosen from the tetrasodium salt of 1-hydroxyethyl-1,1-diphosphonic acid and the heptasodium salt of diethylenetriamine-penta acid (methylphosphonic), and N, N-dicarboxymethyl-2-aminopentane-1,5-dioic acid.

The anti-scaling system may also comprise sodium citrate, preferably in an amount of less than 22% by weight of the detergency builder composition.

This compound also makes it possible to improve the rate of incrustation of the compositions and has the advantage of being completely biodegradable.

The detergent builder composition of the invention can serve as the basis for machine wash compositions by providing both a fully soluble builder system without zeolites or mineral phosphates and an anti-encrustation system.

In this regard, the invention also relates to the use of this detergency builder composition in detergent compositions for washing laundry in the machine.

The invention also relates to a detergent composition without zeolite or mineral phosphate for washing machine in a machine comprising said composition. tion of detergency builder and at least one detergent.

At least one surfactant is present as a detergent, advantageously in an amount which can range from 2 to 10% of the weight of the detergent composition. Among these surfactants, mention may be made of:

- anionic surfactants of the alkali metal soap type (alkaline salts of C ₈ -C ₂₄ fatty acids), alkali sulfonates (C ₈ -C ₁₃ alkylbenzene sulfonates, C ₁₂ -C ₁₆ alkyl sulfonates), alcohols oxyethylenated and sulphated C ₆ -C ₁₆ fatty acids, al C ₈ -C ₁₃ oxyethylenated and sulphated ylphenols, alkali sulfosuccinates (C ₁₂ -C ₁₆ alkyl sulfosuccinates);

- nonionic surfactants of the alkylphenol type C ₆ -C ₁₂ polyoxyethylenated aliphatic alcohols C ₂₂ -C _β oxyéthlénés, block copolymers of ethylene oxide - propylene oxide, has ides optionally polyoxyethylenated carboxylic acids,

surfactants with photers of the alkyl dimethyl betaines type,

- cationic surfactants of the chlorides or bromides of alkyltrimethylammonium, of alkylldimethylethylammonium.

The agents present in the detergency builder composition are found in the final detergent composition at a rate of 30 to 45% of the weight of the latter for the cogranules and from 0.25 to 0.75%, preferably from 0 , 3 to 0.5%, for the phosphonate or the mixture of phosphonates. If free sodium carbonate is also used in the adjuvant composition, it preferably represents less than 7% of the total weight of the detergent composition.

When the adjuvant composition contains a compound or a mixture of organic anti-scaling compounds as mentioned above, it is advantageous that these represent from 2 to 6% by weight total of the detergent composition.

Similarly, when the adjuvant composition contains sodium citrate, it is advantageous that the latter represents less than 7% of the total weight of the detergent composition.

The anti-encrustation system of the detergency builder composition according to the invention is effective for all types of detergent formulations. It is suitable for standard formulations but especially finds its application in formulations of the compact type with a high carbonate content.

The washing compositions according to the invention respect the environment because they contain a detergent agent very low in phosphonates.

A washing composition in accordance with the invention can be prepared by adding to the adjuvant composition at least one detergent such as those indicated above and other conventional components of the detergent compositions for washing clothes.

Thus, the detergent composition can comprise, in addition to the detergency builder composition and the detergent (s):

- detergency builders, such as sodium silicate preferably at a rate of 0.5 to 5% of the total weight of the formulation,

- anti-redeposition agents of the carboxymethylcellulose and methylcellulose type in an amount which can range up to approximately 5% of the total weight of said detergent composition,

- bleaching agents of the perborate, percarbonate, chloroisocyanurate, N, N, N ', N'-tetraacetylethylenediamine (TAED) type up to approximately 30% of the total weight of said detergent composition, - fillers of the type sodium sulphate for powder detergents up to 50% of the total weight of said detergent composition.

The detergent compositions are obtained in a manner known to those skilled in the art. For example, the surfactant is melted, then the other liquid components of the formula are added to it. The liquid is then adsorbed on the rest of the solid constituents and the composition is mixed until homogenization.

The invention is illustrated by the following examples.

EXAMPLE 1

A compact detergent composition is prepared using a cogranule manufactured and marketed by RHONE-POULENC under the brand Nabion 15. It comprises a hydrated sodium silicate with a molar ratio Si0 ₂ / Na ₂ 0 equal to 2, supported by carbonate of sodium, in the following proportions:

Carbonate 56

Silicate 27 Water 17%.

The composition formula is shown below:

anionic surfactant (LABS) 5 nonionic surfactants 3 sodium perborate NaB0 ₃ , 4H ₂ 0 10,, 8 tetraacetyl ethylene diamine 1, 2

Nabion 15 38 sodium carbonate 7 sodium silicate R2 3 sodium sulfate 30, 56 heptasodium salt of diethylene triaminepenta (ethylphosphonic acid) Na ₇ DTPMP 0.64 carboxymethylcellulose o, 5 enzymes o,, 3. The heptasodium salt of diethylene triaminepenta (methylphosphonic) acid Na ₇ TDPMP is marketed by MONSANTO under the brand Dequest 2066 in the form of a solution containing 32% of active material. The rate of calcium encrustation appearing when using this composition is measured as follows.

Washing is carried out in a Tergotometer (U.S. Testing Company, Hobdoken, U.S.A.) which is a reduced reproduction of washing machines used in the U.S.A. This tool can also be used to determine the detergent performance of washing compositions.

The cotton used for the incrustation test is a cotton-polyamide (92% / 8%) known under the name Terry 12 A (Testfabrics). The tissue is depreciated and then introduced at the rate of 5 specimens of size 10 x 12 cm in the tergotometer. The washing is carried out under the following conditions: washing temperature: 60 ^* C number of washes: 6 duration of each washing: 20 minutes stirring: 100 cycles / min detergent concentration: 5 g / 1 water hardness: 39 ° TH (obtained by diluting Contrexéville mineral water at 156 ^th TH).

The incrustation rates are then determined after calcination of the cotton test pieces at 950 ° C. for 3 hours. The ash rate for Terry 12A cotton is 0.28% by weight. The inlay results which will be given later are expressed without deduction of the ash rate.

The reproducibility of the test is determined with a standard deviation of σ = 0.15. COMPARATIVE EXAMPLES 1 to 3

For comparison, three compositions are prepared with the same ingredients as those of the composition of Example 1, in the proportions of the formula of Example 1 while removing the phosphonate.

In Comparative Example 1, the formula is completed 100% with an amount of additional sodium sulfate.

In Comparative Example 2, the phosphonate is replaced by 5% by weight of Sokalan CP5 brand acrylate / sodium maleate copolymer from BASF, the amount of sodium sulphate being reduced accordingly to 100%.

In Comparative Example 3, the phosphonate is replaced by 5% by weight of a sodium polyacrylate of molecular weight 4500, the amount of sodium sulfate being reduced accordingly to reach 100%.

The incrustation rates recorded with these compositions are shown in Table 1 below.

TABLE 1

Composition Example 1 Example Example Comparative Comparative Comparative Example

1 2 3

Anti-incmstant Na ₇ DTPMP CP 5 PA 4500 0.64% 0 5% 5%

Inlays% 1.64 3.21 2.64 2.73

These results show that the anti-scaling effect of the phosphonate in the proportions used is much greater than that of the polymers commonly used.

EXAMPLES 2 and 3 Compositions are prepared using as an anti-encrustation system a mixture of phosphonate Na ₇ DTPMP and of copolymer CP5 used in Comparative Example 2.

The composition of Example 2 contains 0.64% by weight of phosphonate Na ₇ TDPMP and 5% by weight of the copolymer CP5.

The composition of Example 3 contains 0.32% by weight of phosphonate Na ₇ TDPMP and 5% by weight of the copolymer CP5.

The other constituents of the compositions are identical to those of formula 1, they are used in the same proportions except that the amount of sodium sulfate is adjusted in both cases to complete the formula to 100%.

A summary of the formulas and the results Inlay states are shown in Table 2.

TABLE 2

Composition Example 2 Example 3

Anti-scaling

- Na ₇ DTPMP 0.64% 0.32%

- CP5 5% 5%

Inlays% 1.24 1.90

The performance of the composition of Example 2 is comparable to that of a composition of zeolite type with a low carbonate content, containing 5% of conventional polymer CP5.

EXAMPLES 4 to 7

Compositions are prepared using another phosphonate, namely the tetrasodium salt of 1-hydroxyethylene-1,1-diphosphonic acid NaHEDP, marketed by MONSANTO in the form of a solution for

25% under the Dequest 2016 brand.

In Example 4, the composition contains phosphonate alone. In Examples 5 and 6, the compositions contain respectively 0.32% and 0.4% by weight of phosphonate as well as 5% by weight of the copolymer CP5.

The composition of Example 7 contains 0.4% by weight of phosphonate and 5% by weight of a sodium polyaspartate of molecular weight 4500. The other constituents of the compositions are identical to those of formula 1, they are used in the same proportions except that the amount of sodium sulfate is adjusted in each case to complete the formula 100%.

The inlay tests gave the results in Table 3, which reveal in particular the very good performance of a system combining the tetrasodium salt of low-dose 1-hydroxyethylene-1,1-diphosphonic acid NAHEDP and the CP5 polymer.

TABLE 3

Composition Example Example Example Example

4 5 6 7

Anti-scaling

- Na ₄ HEDP 0.4% 0.32% 0.4% 0.4%

- CP5 0 5% 5% 0%

- Sodium polyaspartate 0 0 0 5%

Inlays% 1.82 1.46 1.12 1.70

EXAMPLES 8 and 9

Detergent compositions are prepared by incorporating sodium citrate which is a trisodium citrate trihydrate Na ₃ C ₆ H ₅ 0 ₇ , 2 H ₂ 0.

The composition of Example 8 contains 0.32% by weight of the phosphonate Na ₄ HEDP and 5% by weight of sodium citrate.

The composition of Example 9 also contains 5% by weight of the copolymer CP5.

The other constituents of the compositions are identical to those of formula 1, they are used in the same proportions except that the amount of sodium sulfate is adjusted in both cases to complete the formula to 100%. A summary of the formulas and the performances of these compositions appear in Table 4.

TABLE 4

Composition Example 8 Example 9

Anti-scaling

- Na ₄ HEDP 0.32 0.32

- Sodium citrate 5 5

- CP 5 0 5

Inlays% 1.49 0.5

These compositions lead to a very low incrustation rate. The presence of sodium citrate also has the effect of improving the detergent properties.

EXAMPLE 10

A detergent composition based on a detergency builder composition containing as a non-encrusting system a mixture of Na ₄ HEDP and acid

N, N-dicarboxymethyl-2-aminopentane-1,5-dioic acid is prepared according to the formula below:

anionic surfactant (LABS) 6 nonionic surfactants 12 sodium perborate NaB0 ₃ , 4H ₂ 0 15 tetraacetyl ethylene diamine 5 Nabion 15 38 sodium carbonate 8 sodium sulfate 7.6 Na ₄ HEDP 0.4 N, N-dicarboxymethyl-2-aminopentane-1,5-dioic acid 5 carboxymethylcellulose 1.5 enzymes 0.3,

This composition is used as a tergotometer to carry out an inlay test, the results of which are given in Table 5.

Comparative example 4

The composition of Example 10 is modified by replacing N, N-dicarboxymethyl-2-aminopentane-1,5-dioic acid with sodium sulfate. The results of the corresponding inlay test are shown in Table 5, which shows the anti-scaling effect of N, N-dicarboxymethyl-2-aminopentane-1,5-dioic acid.

TABLE 5

COMPOSITION Example 10 Comparative example 4

Anti-scaling

- Na ₄ HEDP 0.4 0.4

- N, N-dicarboxymethyl-2-amino-pentane- 1,5-dioic acid 5 0

Inlays% 1.19 1.88

Claims

1. A detergency builder composition comprising, on the one hand, a fully soluble adjuvant system without zeolite or mineral phosphates, based on cogranules comprising an alkali metal carbonate, an alkali metal silicate nSi0 ₂ -M ₂ 0, where M represents an alkali metal and the molar ratio Si0 ₂ / M ₂ 0 = n is 1.5 to 3.5, and water associated with silicate, the weight ratio (water associated with silicate) / (silicate expressed in sec) being greater than 33/100, and, on the other hand, an anti-encrustation system comprising a phosphonate or a mixture of organic phosphonates in an amount such that the weight ratio (phosphonate) / (carbonate) is from 0.007 to 0, 05.

2. Composition according to claim 1, in which the weight ratio (phosphonate) / (carbonate) is from 0.01 to 0.03.

3. Composition according to claim 1 or 2, in which the cogranules of the adjuvant system comprise sodium carbonate and sodium silicate.

4. Composition according to one of claims 1 to 3, in which the organic phosphonate is chosen from amino-tris-methylene-phosphonic acid and its pentasodium salt, 1-hydroxyethylene-l, 1-diphosphonic acid and its tetrasodium salt, ethylene diamine-tetra- (methylphosphonic acid) and its pentasodium salt, the hexapotassium salt of hexamethylenedia- mine-tetra (methylphosphonic acid), and diethylene triamine-penta acid ( methylphosphonic), and its heptasodic salt.

5. Composition according to one of claims 1 to 4, wherein the anti-encrustation system further comprises a compound or a mixture of compounds organic selected from copolymers of acrylic acid and maleic anhydride and the sodium salts thereof, sodium polyacrylates, sodium polyaspartate, polysuccinimide, polyimides derived from amino acids and their hydrolysates, the acid N, N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and the salts derived therefrom, in a proportion of 2 to 20% by weight.

6. Composition according to claim 5, in which the anti-encrustation system comprises a mixture of an organic phosphonate chosen from the tetrasodi¬ salt as 1-hydroxyethylene-l, 1-diphosphonic acid and the heptasodic salt of the diethylenetriamine-penta (methylphosphonic) acid and an acrylate / sodium maleate copolymer.

7. Composition according to claim 5, in which the anti-encrustation system comprises a mixture of an organic phosphonate chosen from the tetrasodi¬ salt as 1-hydroxyethylene-l, 1-diphosphonic acid and the heptasodic salt of the diethylenetriamine-penta (methylphosphonic) acid and N, N-dicarboxymethyl-2-aminopentane-1,5-dioic acid.

8. Composition according to one of claims 1 to 7, wherein the anti-encrustation system further comprises sodium citrate in an amount of less than 22% by weight.

9. Use of a composition 'detergency builder according to any one of claims 1 to 8 as an anti-scaling adjuvant system in a composition for washing laundry in the machine.

10. Detergent composition without zeolite or mineral phosphates comprising at least one deter¬ gent agent and a detergency builder composition according to any one of claims 1 to 8 as an anti-encrusting builder system.

11. Composition according to claim 10, in which the cogranules of the detergency builder composition represent from 30 to 45% by weight of the detergent composition, and the phosphonate or the mixture of phosphonates represents from 0.25 to 0.75% by weight of the detergent composition.

12. Detergent composition according to claim 10 or 11, comprising a detergency builder composition according to any one of claims 5 to 8, in which said compound or said mixture of organic compounds represents from 2 to 6% by weight of the detergent composition.

13. Detergent composition according to one of claims 10 to 12, comprising a detergency builder composition according to claim 8, wherein the sodium citrate represents less than 7% by weight of the detergent composition.