USE IN DETERGENT COMPOSITIONS OF POLYMERS OBTAINED BY LOW-CONCENTRATION REVERSE EMULSION POLYMERIZATION WITH A LOW CONTENT OF NEUTRALIZED MONOMERS

Abstract

An aqueous liquid detergent composition for household or industrial use, of a branched or cross-linked polymer is obtained by polymerizing an aqueous solution of one or more monomers by water-in-oil reverse emulsion, at least one of the monomers used being an acrylic monomer and one or more of the monomers used being a monomer carrying at least one weak acid function. The molar percentage of monomers carrying at least one weak acid function relative to the totality of the monomers being used being at least 30%, characterized in that: i) the polymerization is carried out with a concentration of the totality of the monomers in aqueous solution being in the range 1.3 mmol to 3.6 mmol per gram of aqueous solution; ii) during the polymerization, at most 20% of the acid functions present on the monomers having at least one acid function are in the neutralized form.

Claims

1. Use, for the manufacture of an aqueous liquid detergent composition for household or industrial use, of a branched or cross-linked polymer composed by repeating one or more monomeric units, with at least one of the monomeric units corresponding to a monomer comprising an acrylic group and at least 30 mol % of the monomeric units carrying at least one weak acid function that is optionally in the neutralized form, said polymer being obtained: by polymerizing an aqueous solution of one or more monomers by water-in-oil reverse emulsion, at least one of the monomers used being an acrylic monomer and one or more of the monomers used being a monomer carrying at least one weak acid function, the molar percentage of monomers carrying at least one weak acid function relative to the totality of the monomers used being at least 30%, the aqueous phase containing at least one monomer acting as a branching agent, in a manner such that the polymerization results in a branched or cross-linked polymer, characterized in that: i) the polymerization is carried out with a total concentration of the monomers in aqueous solution being in the range 1.3 mmol to 3.6 mmol per gram of aqueous solution; ii) during the polymerization, at most 20% of the acid functions present on the monomers having at least one acid function are in the neutralized form.

2. Use, for thickening an aqueous liquid detergent composition for household or industrial use, of a branched or cross-linked polymer composed by repeating one or more monomeric units, with at least one of the monomeric units corresponding to a monomer comprising an acrylic group and at least 30 mol % of the monomeric units carrying at least one weak acid function that is optionally in the neutralized form, said polymer being obtained: by polymerizing an aqueous solution of one or more monomers by water-in-oil reverse emulsion, at least one of the monomers used being an acrylic monomer and one or more of the monomers used being a monomer carrying at least one weak acid function, the molar percentage of monomers carrying at least one weak acid function relative to the totality of the monomers used being at least 30%, the aqueous phase containing at least one monomer acting as a branching agent, in a manner such that the polymerization results in a branched or cross-linked polymer, characterized in that: i) the polymerization is carried out with a total concentration of the monomers in aqueous solution being in the range 1.3 mmol to 3.6 mmol per gram of aqueous solution; ii) during the polymerization, at most 20% of the acid functions present on the monomers having at least one acid function are in the neutralized form.

3. The use according to claim 1, characterized in that the polymer comprises a percentage of neutralized acid functions of 30% to 100% relative to the totality of acid functions present on the polymer, obtained by a step of at least partial neutralization of the acid functions present on the polymer produced after the polymerization and before or after preparation of the composition.

4. An aqueous liquid detergent composition for household or industrial use, comprising at least one branched or cross-linked polymer composed by repeating one or more monomeric units, with at least one of the monomeric units corresponding to a monomer having an acrylic group and at least 30 mol % of the monomeric units carrying at least one weak acid function being at least partially in the neutralized form, the percentage of neutralized acid functions relative to the totality of the acid functions present on the polymer being 30% to 100%, said polymer being obtained: by polymerizing an aqueous solution of one or more monomers by water-in-oil reverse emulsion, at least one of the monomers used being an acrylic monomer and one or more of the monomers used being a monomer carrying at least one weak acid function, the molar percentage of monomers carrying at least one weak acid function relative to the totality of the monomers used being at least 30%, the aqueous phase containing at least one monomer acting as a branching agent, in a manner such that the polymerization results in a branched or cross-linked polymer, characterized in that: i) the polymerization is carried out with a total concentration of the monomers in aqueous solution being in the range 1.3 mmol to 3.6 mmol per gram of aqueous solution; ii) during the polymerization, at most 20% of the acid functions present on the monomers having at least one acid function are in the neutralized form; the polymerization being followed by a step of at least partial neutralization of the acid functions, carried out before or after incorporating the polymer into the composition.

5. (canceled)

6. Use of a composition according to claim 4 for cleaning textile fibers, in particular for washing clothes by hand or in a washing machine or for cleaning hard surfaces such as dishes, furniture, floors, window glass, wood, or metal, in particular for cleaning dishes by hand or in a dishwasher.

7. The use according to claim 1, characterized in that during the polymerization, at most 10%, preferably at most 5%, and preferably at most 2% of the acid functions present on the monomers having at least one acid function are in the neutralized form.

8. The use according to claim 1, characterized in that all of the acid functions present on the monomers are in the free acid form during the polymerization.

9. The use according to claim 1, characterized in that the polymerization is carried out with a total concentration of the monomers in aqueous solution in the range 1.7 mmol to 3.3 mmol per gram of aqueous solution.

10. The use according to claim 1, characterized in that the polymer comprises a molar percentage of monomeric units carrying one or more weak acid function(s), relative to the totality of the monomeric units carrying an acid function of at least 50%, preferably at least 70%, more preferably at least 80%.

11. (canceled)

12. The use according to claim 1, characterized in that the monomeric unit(s) carrying at least one weak acid function in the free form, is(are) selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid, with acrylic acid being preferred.

13. The use according to claim 1, characterized in that the polymer is a copolymer comprising at least one neutral monomeric unit selected from acrylamide, methacrylamide, N,N-dimethylacrylamide, N-vinylmethylacetamide, N-vinylformamide, vinyl acetate, diacetone acrylamide, N-isopropyl acrylamide, N-[2-hydroxy-1,1bis (hydroxymethyl) ethyl] propenamide, (2-hydroxyethyl) acrylate, (2,3-dihydroxypropyl) acrylate, methyl methacrylate, (2-hydroxyethyl) methacrylate, (2,3 dihydroxypropyl) methacrylate and vinylpyrrolidone.

14. (canceled)

15. (canceled)

16. The use according to claim 1, characterized in that the polymer is a copolymer comprising at least one monomeric unit carrying one or more strong acid function(s).

17. The use or the composition according to claim 16, characterized in that the molar percentage of monomeric units carrying one or more strong acid function(s) relative to the totality of the monomeric units is less than 50% and preferably less than 30%.

18. The use or the composition according to claim 16, characterized in that the monomeric unit(s) carrying one or more strong acid function(s), in the free form, is(are) selected from acrylamidoalkylsulfonic acids such as 2-acrylamido-2-methylpropane sulfonic acid.

19. (canceled)

20. The use according to claim 1, characterized in that the branching agent is selected from methylene bisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate, vinyloxymethacrylate, triallylamine, formaldehyde, glyoxal, glycidyl ethers such as ethylene glycol diglycidylether, epoxies, and mixtures thereof.

21. The use according to claim 1, characterized in that the quantity of branching agent is between 5 ppm and 10 000 ppm by weight relative to the total weight of the monomers, and preferably between 100 ppm and 5000 ppm.

22. (canceled)

23. The use according to claim 1, characterized in that the polymerization is carried out with a transfer agent selected from methanol, isopropyl alcohol, sodium hypophosphite, 2-mercaptoethanol, sodium methallylsulfonate, and mixtures thereof.

24. The use or the composition according to claim 23, characterized in that the quantity of transfer agent is between 0 ppm and 5000 ppm by weight relative to the total weight of the monomers, and preferably between 10 ppm and 2500 ppm.

25. The use according to claim 1, characterized in that the polymerization is followed by one or more of the following steps: dilution or concentration of the emulsion obtained; isolation in order to obtain the polymer in the form of a powder.

26. (canceled)

27. The use according to claim 1, characterized in that the composition comprises 0.01% to 10% by weight of branched or cross-linked acrylic polymer relative to the total weight of the composition, and preferably 0.1% to 5% by weight of branched or cross-linked acrylic polymer.

28. The use according to claim 1, characterized in that the composition comprises one or more surfactant(s), preferably selected from anionic and nonionic cleaning surfactants.

29. The use or the composition of claim 28, characterized in that the composition comprises 0.1% to 50% by weight of surfactant(s), preferably selected from anionic and nonionic cleaning surfactants, relative to the total composition weight, and preferably 1% to 30% by weight of surfactant(s), preferably selected from anionic and nonionic cleaning surfactants.

30. (canceled)

31. The use according to claim 1, characterized in that the composition comprises at least one additive selected from: detergent additives, also known as “builders”, anti-soiling agents, antiredeposition agents, bleaching agents, fluorescence agents, foam suppressing agents, enzymes, chelating agents, neutralizing agents and pH-adjusting agents.

32. The use according to claim 1, characterized in that the branched or cross-linked polymer is water-soluble or water-swellable.

Description

I. Examples of the Preparation of an Acrylic Acid/Sodium Acrylate Homopolymer

EXAMPLE 1

[0222] The ingredients of the aqueous phase were placed in a 1 L beaker that was being magnetically stirred: [0223] 150 g glacial acrylic acid; [0224] 605 g deionized water; [0225] 0.023 g sodium hypophosphite (150 ppm/total monomer weight); [0226] 0.10 g sodium diethylenetriamine pentacetate; [0227] 0.075 g methylene bisacrylamide (500 ppm/total monomer weight); [0228] 0.15 g sodium bromate.

[0229] Next, the organic phase was prepared in a 1 L glass reactor with mechanical stirring, using: [0230] 102 g aliphatic hydrocarbon (Isopar L); [0231] 98 g white mineral oil (Marcol 152); [0232] 20 g sorbitol monooleate; [0233] 25 g polymeric stabilizer (Hypermer 1083).

[0234] The aqueous phase was slowly transferred into the organic phase. The pre-emulsion that was thus formed then underwent intense shear for 1 min (Ultra Turrax, IKA).

[0235] The reverse emulsion was then degassed for 30 min by simply bubbling nitrogen through.

[0236] An aqueous solution was then added containing 1.0% by weight of sodium metabisulfite at a flow rate of 2.5 mL/h over a period of 1 h30. Once the maximum temperature had been reached, the temperature of the reaction mixture was maintained for 60 min before cooling.

[0237] Finally, at about 30° C., 40 g of ethoxylated tridecyl alcohol was added (6 moles).

EXAMPLE 2

[0238] The ingredients of the aqueous phase were placed in a 1 L beaker that was being magnetically stirred: [0239] 175 g glacial acrylic acid; [0240] 580 g deionized water; [0241] 0.26 g sodium hypophosphite (150 ppm/total monomer weight); [0242] 0.10 g sodium diethylenetriamine pentacetate; [0243] 0.087 g methylene bisacrylamide (500 ppm/total monomer weight); [0244] 0.15 g sodium bromate;

[0245] Subsequently, in order to prepare the organic phase and to carry out the remainder of the preparation process, the procedure followed was that described in Example 1.

EXAMPLE 3

[0246] The ingredients of the aqueous phase were placed in a 1 L beaker that was being magnetically stirred: [0247] 100 g glacial acrylic acid; [0248] 655 g deionized water; [0249] 0.015 g sodium hypophosphite (150 ppm/total monomer weight); [0250] 0.10 g sodium diethylenetriamine pentacetate; [0251] 0.05 g methylene bisacrylamide (500 ppm/total monomer weight); [0252] 0.15 g sodium bromate;

[0253] Subsequently, in order to prepare the organic phase and to carry out the remainder of the preparation process, the procedure followed was that described in Example 1.

EXAMPLE 4

Neutralization 3.5%/Concentration 2.76

[0254] The same process as that described in Example 1 was carried out, adding 5.83 g of 50% sodium hydroxide solution to the aqueous phase, keeping the weight of the aqueous phase the same by adjusting the quantity of deionized water.

EXAMPLE 5

Neutralization 19%/Concentration 3.5

[0255] The ingredients of the aqueous phase were placed in a 1 L beaker that was being magnetically stirred: [0256] 190 g glacial acrylic acid; [0257] 40 g of 50% sodium hydroxide solution; [0258] 525 g deionized water; [0259] 0.028 g sodium hypophosphite (150 ppm/total monomer weight); [0260] 0.10 g sodium diethylenetriamine pentacetate; [0261] 0.095 g methylene bisacrylamide (500 ppm/total monomer weight); [0262] 0.15 g sodium bromate.

[0263] Subsequently, in order to prepare the organic phase and to carry out the remainder of the preparation process, the procedure followed was that described in Example 1.

Comparative Example 1

[0264] The ingredients of the aqueous phase were placed in a 1 L beaker that was being magnetically stirred: [0265] 50 g glacial acrylic acid; [0266] 705 g deionized water; [0267] 0.075 g sodium hypophosphite (150 ppm/total monomer weight); [0268] 0.10 g sodium diethylenetriamine pentacetate; [0269] 0.043 g methylene bisacrylamide (860 ppm/total monomer weight); [0270] 0.15 g sodium bromate.

[0271] Subsequently, in order to prepare the organic phase and to carry out the remainder of the preparation process, the procedure followed was that described in Example 1.

Comparative Example 2

[0272] The ingredients of the aqueous phase were placed in a 1 L beaker that was being magnetically stirred: [0273] 199 g glacial acrylic acid; [0274] 115 g of 50% sodium hydroxide solution; [0275] 441 g deionized water; [0276] 0.03 g sodium hypophosphite (150 ppm/total monomer weight); [0277] 0.10 g sodium diethylenetriamine pentacetate; [0278] 0.15 g methylene bisacrylamide (750 ppm/total monomer weight); [0279] 0.15 g sodium bromate.

[0280] Subsequently, in order to prepare the organic phase and to carry out the remainder of the preparation process, the procedure followed was that described in Example 1.

Comparative Example 3

[0281] The ingredients of the aqueous phase were placed in a 1 L beaker that was being magnetically stirred: [0282] 199 g glacial acrylic acid; [0283] 556 g deionized water; [0284] 0.03 g sodium hypophosphite (150 ppm/total monomer weight); [0285] 0.10 g sodium diethylenetriamine pentacetate; [0286] 0.1 g methylene bisacrylamide (500 ppm/total monomer weight); [0287] 0.15 g sodium bromate.

[0288] Subsequently, in order to prepare the organic phase, the procedure described in Example 1 was followed.

[0289] The aqueous phase was slowly transferred into the organic phase. The pre-emulsion that was thus formed then underwent intense shear for 1 min (Ultra Turrax, IKA).

[0290] The reverse emulsion was then degassed for 30 minutes by simply bubbling nitrogen through.

[0291] An aqueous solution containing 1.0% by weight of sodium metabisulfite was then added at a flow rate of 2.5 mL/h. Immediately after starting to add this reducing solution, the emulsion destabilized and then coagulated. Polymerization was impossible since the system was not stable.

Comparative Example 4

[0292] The ingredients of the aqueous phase were placed in a 1 L beaker that was being magnetically stirred: [0293] 150 g glacial acrylic acid; [0294] 83 g of 50% sodium hydroxide solution; [0295] 522 g deionized water; [0296] 0.023 g sodium hypophosphite (150 ppm/total monomer weight); [0297] 0.10 g sodium diethylenetriamine pentacetate; [0298] 0.75 g methylene bisacrylamide (500 ppm/total monomer weight); [0299] 0.15 g sodium bromate.

[0300] Subsequently, in order to prepare the organic phase and to carry out the remainder of the preparation process, the procedure followed was that described in Example 1.

Characterization of Polymers

Procedure: Measurement of the Viscosity of the Aqueous Solution of Polymer at Iso-Concentration [0.16% by weight]

[0301] 250 g of deionized water was introduced into a 400 mL beaker then, with mechanical stirring (triple-bladed mixer—500 rpm), was slowly added the desired quantity of reverse emulsion for obtaining a solution containing 0.16% by weight of thickening polymer. The pH was then adjusted to 7±0.1 with sodium hydroxide. At this pH, 100% of the acid functions present on the polymer were neutralized. The solution was left for 15 min with stirring, then allowed to stand for 5 min. The viscosity was then measured with the aid of a type RVT Brookfield viscosimeter using spindle 4 and with a speed of rotation of 20 rpm.

[0302] The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Viscosity 0.16% Example NAF MC in water (cps) 1   0% 2.8 6500 2   0% 3.2 4000 3   0% 1.8 6200 4 3.5% 2.8 6500 5  19% 3.5 2500 Comparative 1   0% 0.9 1700 Comparative 2  52% 3.7 500 Comparative 3   0% 3.7 Emulsion not stable Comparative 4  50% 2.8 1500 NAF: Neutralization of the acid functions (%) at the end of polymerization. MC: Monomer concentration in mmol/g of aqueous phase.

[0303] The polymers used in the context of the invention obtained by the reverse emulsion polymerization process had a much better thickening effect than polymers obtained by reverse emulsion processes not complying with the conditions for the % neutralization before polymerization and monomer concentration.

[0304] The polymers obtained in accordance with the invention were highly efficient at very low concentration.

[0305] The resistance to surfactants was evaluated by using these very polymers in deionized water and in the presence of a surfactant: sodium lauryl ether sulfate (LES), marketed by BASF under the reference Texapon® NSO.

[0306] The polymers were compared with one another and with other commercially available thickening polymers: Acusol®820 (Rhom & Haas), an anionic copolymer based on ethyl acrylate and acrylic acid and containing a hydrophobic monomer, obtained by emulsion polymerization (not reverse), and Carbopol° 676 (Lubrizol), a cross-linked acrylic acid polymer obtained by precipitation polymerization. These commercial products are typically used in detergent compositions as a thickening agent.

[0307] The change in the viscosity of a solution comprising 1% by weight of thickening polymer was studied as a function of the conversion of LES.

[0308] More precisely, 250 g of deionized water was introduced into a 400 mL beaker then, with mechanical stirring (triple-bladed mixer—500 rpm), the quantity of reverse emulsion required to obtain a solution containing 1% by weight of thickening polymer was slowly added. The pH was then adjusted to 7 ±0.1 with sodium hydroxide. At this pH, 100% of the acid functions present on the polymer were neutralized. The LES was added at the desired concentration. The solution was left for 15 minutes with stirring, then left to stand for 5 minutes. The viscosity was then measured with the aid of a type RVT Brookfield viscosimeter with spindle 4 and a speed of rotation of 20 rpm.

[0309] The results obtained as a function of the % by weight of added LES are shown in Table 2.

TABLE-US-00002 TABLE 2 Measurement of viscosity of a solution containing 1% by weight of polymer with added sodium lauryl ether sulfate (LES) MC Viscosity (cps) NAF (mmol/ 0% 5% 10% 20% Ex (%) g) LES LES LES LES 1 0% 2.8 21000 12500 8500 3000 2 0% 3.2 18000 9000 5500 2000 3 0% 1.8 19500 12500 8000 2500 4 3.5%   2.8 21500 13000 9000 3000 5 19%  3.5 25000 13000 7800 3500 Comp.1 0% 0.9 15000 3800 1400 150 Comp.2 52%  3.7 32000 5500 450 50 Comp.3 0% 3.7 NA NA NA NA Comp.4 50%  2.8 20000 3800 1000 150 Carbopol ® NA, 46500 18500 9000 2500 676 polymerization method different Acusol ® NA, 820 polymerization 8000 400 <10 <10 method different NAF: Neutralization of the acid functions (%) at the end of polymerization. MC: Monomer concentration in mmol/g of aqueous phase.

TABLE-US-00003 TABLE 3 Percentage drop in viscosity with the addition of sodium lauryl ether sulfate (LES). Ex 5% LES 10% LES 20% LES 1 −40% −60% −85% 2 −50% −69% −89% 3 −36% −56% −87% 4 −40% −58% −86% 5 −48% −69% −86% Comp. 1 −75% −91% −99% Comp. 2 −83% −98% −99% Comp. 3 NA NA NA Comp. 4 −81% −95% −99% Carbopol ® 676 −60% −81% −95% Acusol ® 820 −95% −99% −99%

[0310] The percentage drop in viscosity corresponds to the ratio between the viscosity termed the initial viscosity of the thickened solution without adding the surfactant minus the viscosity of the solution with added surfactant over the initial viscosity multiplied by 100.

[0311] The polymers of Examples 1 to 5 could produce a smaller drop in viscosity and thus good resistance to surfactants compared with the polymers of the comparative Examples 1 to 4 and with Carbopol® 676 and Acusol® 820.

[0312] The person skilled in the art can readily find the best compromise between the thickening efficiency and the surfactant resistance by using his knowledge to vary the polymerization parameters.

II—Behavior of Polymers in the Presence of a Variety of Surfactants

[0313] The series of tests below consisted in evaluating the viscosity of the solutions of the polymers in accordance with the invention in the presence of a variety of surfactants in routine use in detergent compositions. The same procedure as that which produced the results of Table 2 was carried out. The % by weight of each of the surfactants was 5% (relative to the total weight of the solution).

TABLE-US-00004 TABLE 4 Measurement of the viscosity of a solution containing 1% by weight of polymer with the addition of 5% by weight of various surfactants. Alpha-step Sodium Simulsol SL Sodium Lutensol TO MC-48 (Stepan- lauryl 8 (SEPPIC- Sodium dodecyl 89 sodium ether alkylpoly- lauryl benzene (ethoxylated methylester Ex sulfate glucoside) sulfonate sulfonate alcohol) sulfonate) 1 12500 18500 11000 12000 19500 12200 2 9000 15500 8700 8800 16500 9000 3 12500 17500 10500 11800 17500 12000 4 13000 18500 10500 11000 19000 11800 5 13000 22000 11500 12000 21500 12000 Comp. 1 3800 10000 3000 3300 11000 3500 Comp. 2 5500 24000 5000 5000 25000 5200 Comp. 3 NA NA NA NA NA NA Comp. 4 3800 15000 2900 3200 14500 3400 Carbopol ® 676 18500 36000 17000 17500 37000 17500 Acusol ® 820 400 5700 300 350 5500 400

[0314] The percentage drop in viscosity corresponds to the ratio between the viscosity termed the initial viscosity of the thickened solution without added surfactant minus the viscosity of the solution with added surfactant, over the initial viscosity multiplied by 100.

TABLE-US-00005 TABLE 5 Percentage drop in viscosity with the addition of 5% by weight of various surfactants. Alpha-step Sodium Simulsol SL Sodium Lutensol TO MC-48 (Stepan- lauryl 8 (SEPPIC- Sodium dodecyl 89 sodium ether alkylpoly- lauryl benzene (ethoxylated methylester Ex sulfate glucoside) sulfonate sulfonate alcohol) sulfonate 1 −40% −12% −48% −43% −10% −42% 2 −50% −14% −52% −52% −11% −50% 3 −36% −10% −46% −39% −10% −38% 4 −40% −14% −51% −48% −12% −45% 5 −48% −12% −54% −52% −14% −52% Comp. 1 −75% −33% −80% −78% −27% −77% Comp. 2 −83% −25% −84% −84% −22% −84% Comp. 3 NA NA NA NA NA NA Comp. 4 −81% −25% −86% −84% −22% −83% Carbopol ® 676 −60% −23% −63% −62% −20% −62% Acusol ® 820 −95% −29% −96% −96% −31% −95%

[0315] The polymers of Examples 1 to 5 could produce a very good surfactant resistance compared with the polymers of the comparative Examples 1 to 4 and with Carbopol® 676 and Acusol® 820, even with different surfactants.

III—Efficiency in Detergent Compositions

[0316] The following tests show the advantage of using polymers obtained under concentration and neutralization conditions defined in the context of the invention in detergent compositions. Polymers of this type provide the compositions with good thickening properties and good resistance to the presence of surfactants.

[0317] A laundry detergent was formulated with the reverse emulsion of Example 1 or with Acusol® 820, the market reference for this type of formulation.

[0318] A dishwasher detergent product was formulated with the reverse emulsion of Example 3 and with Carbopol® 676, market reference in this type of formulation. For each of the compositions numbered 1 and 2 below, the preparation protocol applied was as follows:

Composition N° 1: Laundry Detergent

[0319] This formulation corresponded to a base liquid laundry detergent the viscosity of which was controlled by means of the presence of an acrylic polymer. The dosage was adjusted in order to obtain a viscosity of 800 centipoise (cps)±200 cps (Brookfield RVT, 20 rpm, spindle 3)

[0320] The preparation procedure was simple, consisting in adding all of the ingredients of the following formulation, in the order presented in Table 6 below, to a 400 mL beaker in order to obtain 250 g of final solution:

TABLE-US-00006 TABLE 6 % by Ingredients weight Remarks Deionized water QCP 100% Start at 70% and adjust at end of process. Stirring, triple-bladed mixer, 250 rpm Sodium citrate  3.0% Wait for complete dissolution Sodium dodecylbenzene 10.0% Leave solution 15 min sulfonate(surfactant) with stirring Tridececylic alcohol 6  3.0% EO (surfactant) Sodium laureth sulfate   10% 1EO (surfactant) NaOH (50% aqueous [11.0- Add quantity necessary solution) 12.0] to adjust pH to within indicated range Acrylic polymer * X % Quantity to obtain desired viscosity Sodium carbonate 1.0% Wait for complete dissolution Fragrance and 0.25% colorants *The acrylic polymers tested were as follows: Acrylic polymer * Example 1 Acusol ® 820 Dosage as % by weight  1.8  7 of reverse emulsion as prepared or sold commercially % by weight of 50% 30% thickening polymer in reverse emulsion as prepared (Ex 1) or sold commercially (Acusol ® 820) % by weight of polymer  0.9  2.1 in composition Final viscosity (cps) 800 800 Comments Rapid Rapid dispersion of dispersion polymer (<3 min) Increase in viscosity without forming agglomerates

[0321] The polymer of Example 1 could be used to thicken the laundry detergent formulation for laundry containing 23% of surfactant much more effectively compared with Acusol® 820.

Composition N° 2: Liquid Product for Dishwasher

[0322] This formulation corresponded to an opaque liquid “gel” with added bleach for a washing machine, the viscosity of which was controlled by means of the presence of an acrylic polymer. The dosage was adjusted in order to obtain a viscosity of 9000 cps±2000 cps (Brookfield RVT, 20 rpm, spindle 6)

[0323] The preparation procedure was simple, consisting in adding all of the ingredients of the following formulation to a 400 mL in the order shown in Table 7 below in order to obtain 250 g of final solution:

TABLE-US-00007 TABLE 7 % by Ingredients weight Remarks Deionized water QCP 100% Start at 50% and adjust at end of procedure. Stirring, triple-bladed mixer, 500 rpm Acrylic polymer *  3.0% Mix for approximately 30 min Sodium carbonate 10.0% Add slowly at 250 rpm. Sodium silicate 13.0% Leave solution 15 minutes with stirring NaOH (50%)   5% Quantity to obtain a pH in the range 12.0-13.0 Sodium  15% Add slowly and stir until tripolyphosphate powder completely dissolved Sodium lauryl   3% Add slowly and stir for 5 sulfate minutes (surfactant) Sodium   8% Cool viscous solution to hypochlorite a temperature < 30° C. then (12.5% by weight add bleach. in aqueous Stir for 15 minutes solution) *The acrylic polymers that were tested were as follows: Acrylic polymer * Example 3 Carbopol ® 676 Dosage as % by   1.6   0.9 weight of reverse emulsion as prepared (Ex 3) or powder (Carbopol ® 676) % by weight of 50% 100% thickening polymer in reverse emulsion as prepared (Ex 3) or sold commercially (Carbopol ® 676) % by weight of   0.8   0.9 polymer in the composition Final viscosity 9000 8900 (cps) Comments Complete dispersion after minimum of 30 min of stirring

[0324] The polymer of Example 3 was capable of thickening the laundry detergent formulation containing 3% of surfactant much more effectively compared with Carbopol® 676.