WO1986001823A1

WO1986001823A1 - Aqueous thickened cleaning compositions

Info

Publication number: WO1986001823A1
Application number: PCT/FR1985/000257
Authority: WO
Inventors: Alain Lacroix; Elisabeth Roux; Vincent Bourdin; Christian Renault; Michèle Rozat
Original assignee: Lesieur-Cotelle
Priority date: 1984-09-21
Filing date: 1985-09-20
Publication date: 1986-03-27
Also published as: IT1190392B; FI84915C; KR880700055A; FI862045A; DK237886D0; FI84915B; DK237886A; FR2570713A1; NO166192B; FR2570713B1; DK164117C; DK164117B; FI862045A0; SE8602275D0; BE903274A; KR930003244B1; NO861930L; IT8522222A0; SE463565B; NO166192C

Abstract

The composition according to the invention is comprised of a combination of the following essential constituents: A - at least one long chain amine oxide (OA), and B - one or a plurality of surface agents selected among: a - at least one alkyl ether sulfate (AES), particularly lauryl ether sulfate (LES), and b - at least one salt of N-alkyl, N-acyl amino acid combined with: i) at least one AES, particularly one LES, ii) at least one paraffin sulfonate (PS), or iii) mixtures of i) and ii). Application to the cleaning and disinfection of surfaces and more specially of vertical or inclined surfaces.

Description

THICK AQUEOUS CLEANING COMPOSITIONS

The present invention relates to thickened aqueous cleaning compositions, and more particularly to thickened aqueous compositions containing a C10- hypochlorite ion generator in solution. Thickened cleaning compositions have the advantage of better adhering to vertical or inclined surfaces than those which are not thickened, and consequently of exerting a more effective cleaning and disinfecting action on such surfaces, such as for example bowls. toilets, urinals, siphons, etc. With regard more particularly to thickened or viscous liquid compositions containing hypochlorite, in particular an alkaline hypochlorite and preferably sodium hypochlorite, the development of formulas industrial and commercial faces three types of difficulties, which are: - The physical stability of the solution in a single phase, preferably clear; - Chemical stability, that is to say the limitation of retrogradation (reduction over time of the chlorometric degree, or percentage of active chlorine); - The conservation or limitation of the variation in the viscosity of the composition, after manufacture and during storage.

The liquid hypochlorite-based cleaning compositions currently available do not provide a suitable solution to all of these problems, in particular for a high content of hypochlorite, in particular above 20 ° chlorometric.

In addition, when it is desired to perfume such compositions, the introduction of a perfume further amplifies these difficulties and in turn contributes to the destabilization of the formulas or to their loss of viscosity. It has now unexpectedly been found that these difficulties can be resolved by means of compositions comprising an original combination of different surfactants, namely a combination of:

A - At least one long chain amine oxide (OA), and B - One or more surfactants chosen from: a - at least one alkyl ether sulfate (AES), in particular lauryl ether sulfate (LES), and b - at least one salt of N-alkyl, N-acyl amino acid, combined with: i). at least one AES including an LES, ii). at least one paraffin sulfonate (PS), or iii). mixtures of i) and ii).

Cleaning compositions with hypochlorite have already been described comprising surfactants or combinations of surfactants, among other components. Among the related state of the art documents, particular mention should be made of:

- Document GB-1,128,411, which describes detergent bleaching compositions with alkali metal hypochlorite. The objective, namely the preparation of a liquid detergent providing effective bleaching, is resolved by the combination, with the aqueous hypochlorite solution, of a hydrotrope chosen from a benzene- or naphthalene-sulfonate mono- or poly -alkylated and a detergent. The latter can be an amine oxide and / or lauryl ether sulfate, but it is always associated with an at least equivalent amount of the benzene- or naphthalene-sulfonate derivative. In addition, the compositions are not thickened.

- Document FR-1.521.615. which describes a stable detergent composition with hypochlorite, comprising a detergent surfactant and if necessary a hydrotropic detergent. The detergent surfactant can be lauryl ether sulfate, and the hydrotropic detergent can be an alkylarylsulfonate. The compositions are not thickened and their stability in chlorometric degrees is not convincing. - Document GB-1.466.560. which describes a thickened bleaching composition based on an aqueous solution of alkaline hypochlorite, comprising a surfactant of the sarcosinate or alkali metal tauride type and another surfactant chosen from an alkaline soap of C ₈ fatty acid -C ₁₈ , a quaternary ammonium compound, an amine oxide, a betaine, an alkanolamide and their mixtures. The compositions formed have only relative stability, even insufficient for a hypochlorite with a high chlorometric degree.

- Document FR-2,253,826, which describes liquid detergent bleaching compositions comprising an alkaline hypochlorite and a surfactant of the sulfate or carboxylate type of defined formula. The compositions are said to be stable and it is indicated that this would not be the case for aqueous hypochlorite compositions in which lauryl ether sulfate is present. - Document US-4,229,313, which describes cleaning and bleaching compositions comprising an alkali metal hypochlorite and thickened by means of a branched amine oxide of C ₈ -C ₂₂ , and optionally also comprising an oxide linear C ₇ C ₁₉ amine and / or an alkali metal salt of C ₈ -C ₂₀ fatty acid as additional thickening agents. This is a selection of particular amine oxides, proposed as a means providing better thickening than the previously known combination of a conventional amine oxide and an alkali metal salt of fatty acid. - EP-9942, which describes pourable cleaning and scouring compositions, comprising NaOCl, an anionic surfactant, amine oxide, an electrolyte and a suspended particulate abrasive. It is specified that the anionic surfactant is preferably an alkylsulfate, an alkylbenzene sulfonate or a secondary alkane sulfonate, but that ethoxylated surfactants, insufficiently resistant to oxidation by hypochlorite, should be avoided. The corresponding compositions do not have a marked viscosity and have only relative stability.

- EP-21581, which discloses compositions of aqueous thickened bleach-containing alkali metal hypochlorite and wherein the thickening agent is a mixture of at least one amine oxide, C ₁₀ -C ₁ 8 and of a C ₈ -C ₁₂ alkyl sulfate. Such a thickening system absolutely requires a 48-hour rest. minimum of the mixture to be viscosified, which is completely incompatible with an industrial process of preparation in large tonnages and at a reasonable cost.

- Document EP-30401, which describes thickened liquid bleaching compositions containing an alkali metal hypochlorite and a thickening system composed of a mixture of two different surfactants, with, in addition, a pH buffer composed of a salt of a strong base and a weak mineral acid. It is specified in this document that the compositions for which this technical solution is proposed are those having a low chlorometric degree. Different possibilities are mentioned for each of the two surfactants in the aforementioned two surfactant system and preference is given to a mixture of amine oxides and alkali metal soaps of fully saturated C ₈ -C ₁₈ fatty acids. . In addition, the compositions concerned are in fact intended to contain in suspension up to 5% of their weight of insoluble solid particles.

- Document US-4,388,204, which describes thickened aqueous compositions of alkali metal hypochlorite comprising a fully anionic and ternary thickener comprising: A - an alkyl ether sulfate, B - a salt of N-alkyl, N-acyl amino acid, C - an alkyl sulfate, as well as a silicate.

It is clearly stated that it is imperative that the thickener comprises at least one representative of each of the three classes of anionic surfactants (A), (B), (C) above. It is also clearly indicated that the problem posed, to which this composition aims to provide a solution, was specifically that of the precise adjustment of the viscosity characteristic of the hypochlorite compositions intended for unclogging pipes.

- Document EP 110.106, which describes stable aqueous cleaning compositions comprising a hypochlorite and anionic and / or nonionic surfactants and also containing an amorphous calcium-aluminum silicate. The function of this silicate is to keep the insoluble components in stable suspension.

- Document EP-110.544, which describes thickened bleaching compositions comprising an alkali metal hypochlorite and, as as a sole thickening agent, an amine oxide in a straight chain having at least 14 carbon atoms in this straight chain. This solution to the problem of thickening hypochlorite solutions is not significantly better than others; it is apparently recommended by its author for economic reasons.

It emerges from all of the techniques described above that a person skilled in the art was far from having fully satisfactory solutions for solving the problems linked to the thickening of aqueous hypochlorite solutions and to the stabilization of these thickened solutions. On the contrary, it even appears that those skilled in the art, far from being guided towards new paths or improvements by clear and precise indications, were rather deterred from taking certain paths and disturbed by contradictory technical information.

There was therefore still a need for thickened aqueous cleaning compositions containing a C10- hypochlorite ion generator in solution, which can satisfy the acceptability criteria stated above, namely sufficient viscosity and suitable physical and chemical stability, and this more particularly for compositions having a high content of C10- ion generator. The present invention aims to provide such compositions.

The first object of the invention is a thickened cleaning composition comprising, in an aqueous medium: a hypochlorite, in particular an alkali metal hypochlorite, and a combination of: A - at least one long chain amine oxide (OA) and B - one or more surfactants chosen from: a - at least one, alkyl ether sulfate (AES), in particular lauryl ether sulfate (LES), of alkali metal and: b - at least one alkali metal salt of N-alkyl , N-acyl amino acid, combined with: i). at least one AES, in particular an LES ii). at least one paraffin sulfonate (PS), or iii). mixtures of i) and ii), as well as :

- soda,

- optionally at least one mineral salt (eg NaCl, carbonate or others) and - optionally at least one stable perfume in the presence of NaOCl.

The term “long chain amine oxide” is intended to mean more particularly the C ₁₀ -C ₁₈ alkyl di (C ₁ -C ₆ alkyl) amine oxides, and preferably amine oxides comprising two methyl or ethyl groups and one long-chain alkyl group between C ₁₀ and G ₁₈ , the distribution of which is predominantly C ₁₂ .

As regards the alkyl ether sulfate, of which a preferred example is a lauryl ether sulfate, these are alkali metal sulfates of an ethoxylated aliphatic alcohol. More specifically, these are compounds of formula RO (CH ₂ -CH ₂ O) SO ₃ -M ⁺ , in which R can represent an aliphatic group having from 8 to 18 carbon atoms, preferably from 10 to 14 carbon atoms , M being an alkali metal, preferably sodium or potassium, and n being a number from 1 to 6, preferably from approximately 2 to approximately 4.

The paraffin sulfonate component which can enter into the compositions according to the invention is formed in the practice of technical mixtures of secondary alkyl sulfonates having 10 to 20 carbon atoms per molecule, preferably at least 80% and ordinarily at least 90% of the molecules having 10 to 17 carbon atoms. The salts of N-alkyl, N-acyl amino acid are known surfactants which can be represented by the formula:

R ₁ CON (R ₂ ) CH ₂ COOM in which M represents an alkali metal, preferably sodium, R ₁ is an alkyl group, saturated or unsaturated, preferably a saturated alkyl group in straight chain, containing up to 17 atoms of carbon, and more especially of 9 to 13 carbon atoms, and R ₂ is an alkyl group eh C ₁ -C ₄ , in particular a methyl group (in which case the salts are sarcosinates). Preferred are lauroyl-, cocoyl-, myristoyl- and oleovl ................ sodium sarcosinates, and most particularly lauroyl. ................... sodium sarcosinate. Preferably, the constituents of these compositions are in the proportions by weight and in the weight / weight ratios ci after:

.OA: N-alkyl, N-acyl amino acid salt ≥ 1 (in 100% active material (MA)).

.OA: THE .............................................. .............................. ≥ 1.5 (in 100% of MA). .OA: PS .............................................. ................................ ≥ 3, and preferably ≥ 6 if a fragrance is present (in 100% of MY).

.OA (mainly in C ₁₂ ) ................................ ≤ 12% (in 30% of MA) .

.sel of N-alkyl, N-acyl amino acid .... ≤ 5% (in 30% of MA). .NaOH: up to 2% (in 100% of MA) and more advantageously about 1%.

.Perfume: for example 0.25% or less; the incorporation of the perfume into the composition is carried out according to techniques known to those skilled in the art. The hypochlorite titer is preferably from 20 to 48 ° chlorometric or more, and more advantageously from 30 to 40 ° chlorometric.

For the OA: LES ratio, it seems more advantageous to have a ratio of 1.5 to 4 in case a and a ratio ≥ 5 in cases b i) and / or ii).

If desired, the compositions can also contain other optional additives, such as for example dyes, hydrotropes, electrolytes and the like, for which the skilled person is able to determine, on the basis of his knowledge most suitable, nature, proportions and method of introduction.

For the preparation of these compositions, it is advisable to proceed as follows: (N.B.: if it is planned to include a perfume, it is advisable to make a premix OA + perfume). By operating with continuous stirring, sodium hydroxide, water, and possibly mineral salts (if they have not been added to the water beforehand) are added to the hypochlorite, followed by the component OA or OA. + perfume and other surfactants.

Regarding the amount of water added if necessary, we start from the roughly calculated amount in advance and we have just in the end, depending on the chlorometric titer of the hypochlorite and the solution.

By following this procedure and using the following raw materials:. NaOCl having a chlorometric degree of at least 48; . OA predominantly linear in C ₁₂ ; . Na lauryl sarcosinate; . Lauryl ether Na sulfate; and. PS: di (C _14-17 alkyl) Na sulfonate; a number of compositions have been prepared, the characteristics of which are grouped in the attached table, with also the results of the tests of physical stability in a single phase (STAB.PH.), of stability of the titre of hypochlorite ( in chlorometric degrees) and Epprecht viscosity (VTSCO.E). The first three compositions (ref. 1, 2 and 3) had an OA: PS ratio of less than 3. The abbreviation "nd" means: not determined. The absence of a numerical indication in the column STAB.PH. means that the corresponding formulas were still stable in a single phase after more than 28 days at 40 ° C. For comparison, an aqueous hypochlorite composition, having a starting titer of 35.6 ° chloro. and comprising 3% OA at 30% (30 g./kg), 2% NaOH at 30% (20 g./kg), 0.2% fragrance (2 g./kg) and water (qs 100), had as chlorometric title: 25.8 after 7 days at 40 ° C; 21 after 14 days at 40 ° C; 17.5 after 21 days at 40 ° C; but was not thickened.

Claims

1. Thickened cleaning composition comprising, in an aqueous medium, a hypochlorite, in particular an alkali metal hypochlorite, characterized in that it comprises a combination of: A - at least one long-chain amine oxide (OA) and B - one or more surfactants chosen from: a - at least one alkyl ether sulfate (AES), in particular lauryl ether sulfate (LES), of alkali metal and b - at least one alkali metal salt of N-alkyl, N -acyl amino acid of formula R ₁ CON (R ₂ ) CH ₂ COOM in which M represents an alkali metal, preferably sodium, R, is an alkyl group, saturated or unsaturated, preferably an alkyl group saturated in a straight chain, containing up to 17 carbon atoms, and more particularly from 9 to 13 carbon atoms, and R ₂ is a C ₁ -C ₄ alkyl group, in particular a methyl group, combined with: i). at least one AES, in particular an LES, ii). at least one paraffin sulfonate (PS), or iii). mixtures of i) and ii), as well as:

- soda,

- at least one mineral salt, and

- optionally at least one stable perfume in the presence of NaOCl.

2. Composition according to claim 1, characterized in that it comprises a combination of:

A - at least one long chain amine oxide (OA) and B - b - at least one alkali metal salt of N-alkyl, N-acyl amino acid of formula R ₁ CON (R ₂ ) CH ₂ COOM in which M represents an alkali metal, preferably sodium, R ₁ is an alkyl group, saturated or unsaturated, preferably an alkyl group saturated in a straight chain, containing up to 17 carbon atoms, and more especially from 9 to 13 atoms of carbon, and R ₂ is a C ₂ -C ₄ alkyl group, combined with: i). at least one AES, in particular an LES, ii). at least one paraffin sulfonate (PS), or iii). mixtures of i) and ii), as well as: - soda,

- at least one mineral salt, and

- optionally at least one stable perfume in the presence of NaOCl.

3. Composition according to one of claims 1 or 2, characterized in that the amine oxide is a C ₁₀ -C ₁₈ alkyl di (alkyl in

C ₁ -C ₆ ) amino oxide.

4. Composition according to claim 3, characterized in that the amine oxide comprises two methyl or ethyl groups and a long chain alkyl group between C ₁₀ and C ₁₈ whose distribution is predominantly C ₁₂ .

5. Composition according to one of claims 1 or 2, characterized in that the alkyl ether sulfate is a compound of formula RO (CH ₂ -CH ₂ O) _n SO ₃ -M ⁺ , in which R can represent a group aliphatic having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, M being an alkali metal, preferably sodium or potassium, and n being a number from 1 to 6, preferably from about 2 to about 4.

6. Composition according to one of claims 1 or 2, characterized in that the paraffin sulfonate is formed from technical mixtures of secondary alkyl sulfonates having 10 to 20 carbon atoms per molecule, preferably at least 807. and usually at least 90% of molecules having 10 to 17 carbon atoms.

7. Composition according to one of claims 1 or 2, characterized in that the salt of N-alkyl, N-acyl amino acid corresponding to the above formula is chosen from lauroyl-, cocoyl-, myristoyl- and oleoyl sarcosinates of sodium.

8. Composition according to one of claims 1 or 2, characterized in that its main constituents are in the proportions by weight and in the weight / weight ratios below:

. OA: salt of N-alkyl, N-acyl amino acid% 1 (in 1007. of active material (MA))

. OA: LES ≥ 1.5 (in 100% AD)

. OA: PS ≥3, and preferably ≥6 if a perfume is present (in 100% of

MY)

. OA (mainly in C ₁₂ ) ........................... ≤ 12% (in 30% of MA). salt of N-alkyl, N-acyl amino acid ... ≤ 5% (in 30% of MA). NaOH: up to 27, (in 100% of MA) and more advantageously around 1%.

9. Composition according to one of claims 1 or 2, characterized in that the OA: LES ratio is 1.5 to 4 in case a, and ≥ 5 in cases b i) and / or ii).

10. Composition according to one of claims 1 or 2, characterized in that the title in hypochlorite is from 20 to 48 ° chlorometric or more, and more advantageously from 30 to 40 ° chlorometric.