Detergent composition comprising an inverse latex comprising a particular sequestrant and a polyelectrolyte combining a strong acid function and a weak acid function

Abstract

Detergent composition (F) for domestic or industrial use including, as thickener, a self-invertible inverse latex including an aqueous phase including: a) a crosslinked anionic polyelectrolyte (P) consisting of: at least one first monomer unit derived from 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid in free acid form or partially or totally salified form; and at least one second monomer unit derived from at least one monomer chosen from the elements of the group consisting of acrylic acid, methacrylic acid, 2-carboxyethylacrylic acid, itaconic acid, maleic acid, 3-methyl-3-[(1-oxo-2-propenyl)amino]butanoic acid, the carboxylic function of the monomers being in free acid, partially salified or totally salified form; at least one third monomer unit derived from a polyethylenic crosslinking monomer (AR), b) ethylenediaminedisuccinic acid in trisodium salt form.

Claims

1. Detergent composition (F) suitable for domestic or industrial use comprising, as thickener, a self-invertible inverse latex comprising an aqueous phase comprising: a) a crosslinked anionic polyelectrolyte (P) consisting of: at least one first monomer unit derived from 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid in free acid form or partially or totally salified form; and at least one second monomer unit derived from at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, 2-carboxyethylacrylic acid, itaconic acid, maleic acid, 3-methyl-3-[(1-oxo-2-propenyl)amino]butanoic acid, the carboxylic function of said monomers being in free acid, partially salified or totally salified form; at least one third monomer unit derived from a polyethylenic crosslinking monomer (AR), b) ethylenediaminedisuccinic acid in trisodium salt form.

2. The detergent composition according to claim 1, wherein the aqueous phase of the inverse latex comprises at least 0.01 mol % of ethylenediaminedisuccinic acid in trisodium salt form.

3. The detergent composition according to claim 1, wherein the polyethylenic crosslinking monomer (AR) is chosen from methylenebis(acrylamide), ethylene glycol dimethacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate, diallylurea, triallylamine, trimethylolpropane triacrylate, diallyloxyacetic acid or a salt thereof, or a mixture of these compounds.

4. The detergent composition according to claim 1, wherein the crosslinking monomer (AR) is methylenebis(acrylamide) or triallylamine.

5. The detergent composition according to claim 1, wherein the crosslinked anionic polyelectrolyte of the aqueous phase of the inverse latex comprises: a proportion between 20% and 90% of the monomer unit derived from 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid in free acid form or partially or totally salified form; and a proportion between 10% and 80% of the monomer unit derived from at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, 2-carboxyethylacrylic acid, itaconic acid, maleic acid, 3-methyl-3-[(1-oxo-2-propenyl)amino]butanoic acid, the carboxylic function of said monomers being in free acid, partially salified or totally salified form; a proportion of greater than 0 mol % and less than or equal to 1 mol % of monomer units derived from at least one polyethylenic crosslinking monomer (AR).

6. The detergent composition according to claim 1, comprising between 0.1% and 10% by weight of said self-invertible inverse latex.

7. A thickener and/or emulsifier and/or stabilizer for a detergent liquid aqueous composition suitable for domestic or industrial use, comprising the inverse latex of claim 1.

8. The detergent composition according to claim 1, wherein the polyethylenic crosslinking monomer (AR) is sodium diallyloxyacetate.

9. The detergent composition according to claim 2, wherein the polyethylenic crosslinking monomer (AR) is chosen from methylenebis(acrylamide), ethylene glycol dimethacrylate, diethylene glycol diacrylate, ethylene glycol diacrylate, diallylurea, triallylamine, trimethylolpropane triacrylate, diallyloxyacetic acid or a salt thereof.

10. The detergent composition according to claim 2, wherein the crosslinking monomer (AR) is methylenebis(acrylamide) or triallylamine.

11. The detergent composition according to claim 3, wherein the crosslinking monomer (AR) is methylenebis(acrylamide) or triallylamine.

Description

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(1) The examples that follow illustrate the invention without, however, limiting it.

Examples

(2) 1.1 Preparation of an Inverse Latex (LI.sub.1) Comprising a Crosslinked Copolymer of the Sodium Salt of 2-Methyl-[(1-Oxo-2-Propenyl)Amino]-1-Propanesulfonic Acid and of Acrylic Acid Partially Salified in Sodium Salt Form Containing Ethylenediaminedisuccinic Acid in Trisodium Salt Form as Sequestrant.

(3) The following are charged to a beaker, with stirring: 277 grams of deionized water, 73.1 grams of glacial acrylic acid, 308 grams of 2-methyl-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, 141 grams of an aqueous 48 wt % solution of sodium hydroxide, 0.62 gram of a commercial 35 wt % solution of ethylenediaminedisuccinic acid in trisodium salt form (sold under the brand name Natriquest? E30), 0.128 gram of methylenebis(acrylamide), 0.1 gram of copper sulfate pentahydrate (i.e. an amount of 160 molar ppm relative to the sum of the number of moles of 2-methyl-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid and of the number of moles of acrylic acid).

(4) The pH of the aqueous phase is adjusted to 5.4 and the solution is made up with deionized water to 682 g.

(5) The organic phase is prepared at the same time: 220 grams of isohexadecane, 25 grams of Montane? 80, 0.2 gram of azobis(isobutyronitrile) (AIBN).

(6) The aqueous phase prepared above is gradually added to the oily phase and then dispersed using a rotor-stator of Ultra Turrax? type sold by the company IKA.

(7) The emulsion obtained is then transferred to a jacketed reactor, and subjected to nitrogen bubbling in order to remove the oxygen. A solution containing 0.42% by weight of cumene hydroperoxide in isohexadecane is introduced and the emulsion is kept stirring for 5 minutes of homogenization at room temperature.

(8) An aqueous solution of 0.1% sodium metabisulfite in 25 g of water is introduced using a pump with a flow rate of 0.5 ml/minute in order to initiate the polymerization reaction. The temperature of the medium will increase until a plateau is reached. The reaction medium is then heated at 85? C. for 1 h and then the whole medium is cooled to around 35? C., and 50 g of Polysorbate 80 sold under the brand name Montanox? 80 are added.

(9) The resulting self-invertible inverse latex is evaluated by observation of its appearance at 25? C., by its viscosity at 25? C., by the viscosity of an aqueous gel containing 2 wt % of a self-invertible inverse latex, by the viscosity of an aqueous gel containing 3 wt % in the presence of 0.1 wt % of sodium chloride.

(10) This test is referenced (LI.sub.1).

(11) The results obtained are given in table 1 below.

(12) 1.2 Preparation of an Inverse Latex (Liz) Comprising a Crosslinked Copolymer of the Sodium Salt of 2-Methyl-[(1-Oxo-2-Propenyl)Amino]-1-Propanesulfonic Acid and of Partially Salified Acrylic Acid Containing Sodium Diethylenetriaminepentaacetate as Sequestrant.

(13) The same protocol as in the preceding example using 0.45 g of a solution containing 40% by weight of sodium diethylenetriaminepentaacetate (sold under the brand name Versenex? 80) instead of the solution of ethylenediaminedisuccinic acid in trisodium salt form.

(14) This test is referenced (LI.sub.2).

(15) 1.3 Preparation of an Inverse Latex (LI.sub.3) Comprising a Crosslinked Copolymer of the Sodium Salt of 2-Methyl-[(1-Oxo-2-Propenyl)Amino]-1-Propanesulfonic Acid and of Partially Salified Acrylic Acid Containing Glutamic Acid, N,N-Diacetic Acid, Tetrasodium Salt as Sequestrant.

(16) The same protocol as in example 1.1 is used, using 2 g of a solution containing 47% by weight of the glutamic acid, N,N-diacetic acid, tetrasodium salt (sold under the brand name Dissolvine? GLDA 47-S) instead of the solution of ethylenediaminedisuccinic acid in trisodium salt form.

(17) This test is referenced 14654 MP.

(18) 1.4 Preparation of an Inverse Latex (LI.sub.4) Comprising a Crosslinked Copolymer of the Sodium Salt of 2-Methyl-[(1-Oxo-2-Propenyl)Amino]-1-Propanesulfonic Acid and of Partially Salified Acrylic Acid.

(19) The same protocol as in example 1.1 is used, without using sequestrant.

(20) The test is referenced (LI.sub.4).

(21) 1.5 Preparation of an Inverse Latex (LI.sub.5) Comprising a Crosslinked Copolymer of the Sodium Salt of 2-Methyl-[(1-Oxo-2-Propenyl)Amino]-1-Propanesulfonic Acid and of Partially Salified Acrylic Acid Containing Ethylenediaminedisuccinic Acid in Trisodium Salt Form as Sequestrant.

(22) The same protocol as in example 1.1 is used, while reducing the amount of sequestrant to 0.15 g of ethylenediaminedisuccinic acid in trisodium salt form.

(23) The test is referenced (LI.sub.5).

(24) 1.6 Preparation of an Inverse Latex (LI.sub.6) Comprising a Crosslinked Copolymer of the Sodium Salt of 2-Methyl-[(1-Oxo-2-Propenyl)Amino]-1-Propanesulfonic Acid and of Partially Salified Acrylic Acid Containing Ethylenediaminedisuccinic Acid in Trisodium Salt Form as Sequestrant and without Addition of CuSO4.

(25) The copolymer was prepared following the same protocol as example 1.1 but without adding copper sulfate, therefore without adding a Cu.sup.2+ salt.

(26) The test is referenced (LI.sub.6).

(27) TABLE-US-00001 TABLE 1 Characterizations Viscosity of Viscosity of Viscosity aqueous gel aqueous gel of latex containing containing at 25? C., 2 wt %, 3 wt % + 0.1% Sequestrant mPa .Math. s mPa .Math. s NaCl, mPa .Math. s (amount in Polymerization (Brookfield RVT, (Brookfield RVT, (Brookfield RVT, Test molar ppm) Inhibition Exothermicity Polymerization Spindle 3 Spindle 6 Spindle 6 no (*) (min) (? C.) time (min) Speed 20) Speed 5) Speed 5) (LI.sub.4) / 33 No initiation of polymerization (LI.sub.2) Versenex? 0 34 16 910 97 000 6000 80 (150 ppm) (LI.sub.1) Natriquest? 0 34.3 15 1000 77 000 6800 E30 (250 ppm) (LI.sub.3) Dissolvine? 0 14.6 28 nr nr nr GLDA 47-S (1137 ppm) (LI.sub.5) Natriquest? No initiation of polymerization E30 (60 ppm) (LI.sub.6) Natriquest? 1 35.8 15 830 68 000 4800 E30 (250 ppm) Properties of the copolymers obtained in examples 1.1, 1.2, 1.3, 1.4, 1.5 and 1.6. (*): The amount of sequestrant is expressed in molar ppm and calculated relative to the molar sum of the two monomers (2-methyl-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid and acrylic acid).

(28) Test (LI.sub.4) shows the impact of the proven presence of metal cations on the progression of the polymerization process: in the presence of copper cations (in this case at least 160 molar ppm of Cu ions) and in the absence of any sequestrant, the polymerization reaction does not take place. The introduction of the sodium diethylenetriaminepentaacetate (sold under the brand name Versenex? 80) in test (LI.sub.2) allows the polymerization reaction to take place and leads to a polymer being obtained that has thickening properties in water and in saline solution.

(29) In comparison, the use of ethylenediaminedisuccinic acid in trisodium salt form (sold under the brand name Natriquest? E30) in test (LI.sub.1), under stoichiometric conditions identical to test (LI.sub.2), makes it possible to obtain similar polymerization kinetics and a self-invertible inverse latex that has an equivalent viscosifying performance. As test (LI.sub.5) shows, the amount of ethylenediaminedisuccinic acid in trisodium salt form must be high enough: introduced at a lower dose (60 molar ppm), it does not make it possible to complex all of the cations, which results in the absence of initiation of the polymerization. Furthermore, test (LI.sub.6), free of added copper cations, shows that the process takes place in an identical manner: ethylenediaminedisuccinic acid in trisodium salt form as is has no impact on the polymerization reaction.

(30) Test (LI.sub.3) demonstrates the lower efficacy of the glutamic acid, N,N-diacetic acid, tetrasodium salt (sold under the brand name Dissolvine? GLDA 47-S), despite its higher chelating capacity (85 milligram of Cu/gram of sequestrant [1]) than that of ethylenediaminedisuccinic acid in trisodium salt form (18.4 milligrams of Cu/gram of sequestrant [2]). Specifically, added before the polymerization under identical stoichiometric conditions, glutamic acid, N,N-diacetic acid, tetrasodium salt enables the initiation of the polymerization reaction but the kinetics are slower than in test (LI.sub.2) and than in test (LI.sub.1): the reaction time is almost two times longer. Likewise, the exothermicity observed is lower, which suggests that the conversion of the monomers is not complete. The process has not therefore taken place properly. [1]: Data sheet: https://chelates.nouryon.com/globalassets/inriver/resources/pds-dissolvine-gl-47-s-en-201907030902.pdf [2]: http://www.innospecinc.com/assets/_files/documents/may_08/cm_1210345005_NatrIquest_E30.pdf [3]: http://www.kalekimya.com/admin/tds/1417095773_VERSENEX_80_E_TDS.pdf
II: Illustrative Detergent Formulations

(31) In the formulations below, the percentages are expressed as weight percentages per 100% of the weight of the formulation.

(32) II.sub.ACleaning Composition for Ovens and Cooking Grills

(33) TABLE-US-00002 Ingredients Weight content SIMULSOL?OX1309L.sup.(1) 2% SIMULSOL?SL7G.sup.(2) 2% Composition (LI.sub.6) 6% Sodium hydroxide: 25% Water: qs 100% .sup.(1)Simulsol? OX1309L: detergent surfactant composition sold by the company SEPPIC, comprising polyethoxylated alcohols resulting from the reaction of 1 molar equivalent of an alcohol sold under the brand name Exxal?13 with 9 molar equivalents of ethylene oxide. .sup.(2)Simulsol?SL7G: solution of n-heptyl polyglucosides, hydrotropic and solubilizing agent sold by the company SEPPIC.
Preparation

(34) a) A pre-gel is prepared at 20? C. by adding Simulsol? OX1309L and then Simulsol? SL7G in water. Composition (LI.sub.6) according to the invention is then introduced into the aqueous solution and mixed until a gel of stable viscosity is obtained.

(35) b) Sodium hydroxide is then gradually introduced with mechanical stirring at a temperature of 20? C. until a homogeneous gel is obtained. The gel obtained on conclusion of step b) is of homogeneous and clear appearance, with a viscosity of 10 000 mPa.Math.s (Brookfield LVT at a speed of 6 rpm). After a period of storage of 6 months at 25? C., the gel obtained on conclusion of step b) of this procedure has a homogeneous and clear appearance, with a viscosity of 12 000 mPa.Math.s (Brookfield LVT at a speed of 6 rpm).

(36) Cleaning Process

(37) The composition prepared above is sprayed at room temperature onto the walls of an oven soiled with food grease and onto cooking grills also soiled with food grease. After 10 minutes, the walls of the oven and the cooking grills are rinsed with hot water at 60? C. The walls of the oven and the surfaces of the cooking grills thus cleaned no longer have any soiling.

(38) II.sub.BCleaner for Aluminium Surfaces

(39) TABLE-US-00003 Ingredients Weight content Simulsol?OX1309L 3% Simulsol?SL7G 3% Composition (LI.sub.6) 5% 75% Phosphoric acid 40% Hordaphos.sup.(3) MDGB 1% 5% Dipropylene glycol methyl ether 5% Water: qs 100% .sup.(3)Hordaphos? MDGB is a composition based on phosphoric esters, used as an anticorrosion agent.
Preparation

(40) Each ingredient is successively introduced into a mixing tank with moderate mechanical stirring, at room temperature, until a homogeneous, clear composition is obtained. Stirring is maintained for 30 minutes at 20? C. The composition obtained has a measured pH value of less than 1.0 and is clear and homogeneous after storage for a period of one month at 40? C.

(41) Cleaning Process

(42) The composition prepared in the preceding paragraph is diluted to 3% in water and the solution thus obtained is sprayed onto the aluminium wall to be cleaned. This wall is then rinsed with hot water at 60? C.

(43) The definitions of the products used in the examples are as follows:

(44) Micropearl? M 100 is an ultrafine powder which is very soft to the touch and which has a mattifying action, sold by the company Matsumo.

(45) Sepicide? CI, imidazolidinyl urea, is a preservative sold by the company SEPPIC.

(46) Simulsol? 165 is self-emulsifying glycerol stearate, sold by the company SEPPIC.

(47) Sepicide? HB, a mixture of phenoxyethanol, methylparaben, ethylparaben, propylparaben and butylparaben, is a preservative sold by the company SEPPIC.

(48) Parsol? MCX is octyl para-methoxycinnamate, sold by the company Givaudan.

(49) Lanol? 37T is glycerol triheptanoate, sold by the company SEPPIC.

(50) Solagum? L is a carrageenan, sold by the company SEPPIC.

(51) Eusolex? 4360 is a sunscreen, sold by the company Merck.

(52) Deepaline? PVB is an acylated wheat protein hydrolysate, sold by the company SEPPIC.

(53) Primol? 352 is a mineral oil, sold by the company Exxon.

(54) Pecosil? PS 100 is Dimethicone PEG-7, sold by the company Phoenix.

(55) Montanov? 68 (INCI name: cetearyl alcohol (and) cetearyl glucoside) is an emulsifier, sold by the company SEPPIC.

(56) Montanov? L (INCI name: C14-22 alcohols (and) C12-20 alkyl glucoside) is an emulsifier sold by the company SEPPIC.

(57) Montanov? 202 (INCI name: arachidyl alcohol (and) behenyl alcohol (and) arachidyl glucoside) is an emulsifier, sold by the company SEPPIC.