EP0165885B1 - Liquid composition for the cleaning of hard surfaces - Google Patents

Description

The present invention relates to a composition for cleaning hard surfaces. It relates more particularly to a composition for cleaning hard surfaces in concentrated liquid form, which can be used as it is or in a diluted form incorporating complementary water. Advantageously, the composition is a clear solution, stable in one phase.

• - les poudres à récurer,
• - les crèmes avec abrasif fin,
• - les liquides.

There are traditionally three categories of cleaning products for hard surfaces, namely:

• - scouring powders,
• - creams with fine abrasive,
• - liquids.

The composition according to the invention belongs to this third category. It includes phosphoric esters.

Many liquid compositions for cleaning hard surfaces have already been described. These compositions have for the most part a relatively low content of active components (on average 15-20% by weight of active components relative to the weight of the composition) and comprise a high proportion of water. Documents DE-A-2 603 307 and FR-A-2 396 797 describe cleaning compositions comprising phosphoric esters; it is specified that these compositions must be acidic so that they give the drying a good surface gloss on the articles cleaned.

In documents FR-A-2 027 559 and FR-A-2 394 602 are described phosphoric esters, presented as useful for the solubilization and respectively the dispersion of insoluble hydrocarbons in aqueous medium. In document FR-A-2 193 871, a single-phase liquid detergent containing, among other things phosphoric esters, is described. However, it is taught therein that the detergent composition must comprise a major proportion of water and that the phosphoric esters recommended have the function of promoting the softening of fabrics, it being specified that the detergent compositions containing them are essentially intended for washing laundry with softening.

Detergent compositions with phosphoric esters for cleaning household utensils or solid surfaces are also described in documents FR-A-2 359 893 and EP-A-94 119. However, phosphoric esters are only adjuvants or reinforcers of detergency in these compositions; presented as such among other possible compounds, it is not they which have the preference. In addition, the detergent compositions do not include non-ionic surfactants, but include amine oxides among the essential constituents.

In document FR-A-2 118 472 are described compositions for washing cars in tunnel type washing stations, combining a nonionic surfactant of formula defined with the phosphoric ester of this same surfactant. active nonionic and with an anionic surfactant obligatorily of the alkyl (linear) benzenesulfonate type.

On the other hand, the document DE-A-2 008 777 describes a composition of surfactants making it possible to obtain controlled foam properties, which is a determining criterion for machine uses, where washing is carried out with intense mechanical agitation.

In this composition, phosphoric esters are combined with nonionic surfactants chosen in a limiting manner to together perform a foam inhibiting function, and these components are combined with an anionic foaming surfactant, so that the composition overall result is a foaming composition with regulated foam height.

The anionic surfactant necessarily includes a sulfate or a sulfonate.

This document teaches that the desired functions are all the better satisfied since the phosphoric esters, which are more precisely alkyl ether phosphates, have a low number (that is to say less than 2 according to the examples) of oxide groups of alkylene and a chain length of the esterifying alkyl group as large as possible (that is to say at least C ₁₈ according to the examples illustrating these requirements). Considerations of the same type, applied to a powder composition for washing products with low foaming power, are developed in document FR-A-2 318 921.

Despite these proposals, which are somewhat contradictory, there is therefore a need for detergent compositions capable of cleaning hard surfaces and removing all types of soiling and particulate soiling, without scratches and in liquid form and preferably in single phase.

We have now unexpectedly found that this objective, and others which will appear on reading the description below, can be achieved by means of a composition combining phosphoric esters and an appropriate combination of other components. with detergent or detergency enhancing action, as active material, in an aqueous medium.

The percentages which are indicated are understood by weight, relative to the total weight of the composition, unless otherwise stated.

• a) au moins deux agents de surfaces anioniques, et parmi eux au moins un savon et au moins un ester phosphorique choisi parmi les esters phosphoriques oxyalkylénés ou alkyl éther phosphates, dans lesquels la chaîne alkyle du groupement estérifiant comprend entre 8 et 12 atomes de carbone et dont le groupement oxyalkylène ou éther comprend de 2 à 18 groupes oxyéthylène et/ou oxypropylène, sous forme de leurs sels de sodium, de potassium ou d'alcanolamine,
• b) au moins un agent de surface non ionique,
• c) au moins un sel alcalin,
• d) au moins un séquestrant,
• e) éventuellement des parfums et/ou des colorants et/ou d'autres additifs compatibles, et
• f) de l'eau pour le complément,

Thus the subject of the invention is an alkaline liquid composition, dilutable with water, for cleaning hard surfaces, characterized in that it comprises:

• a) at least two anionic surfactants, and among them at least one soap and at least one phosphoric ester chosen from oxyalkylenated phosphoric esters or alkyl ether phosphates, in which the alkyl chain of the esterifying group comprises between 8 and 12 carbon atoms and the oxyalkylene or ether group of which comprises from 2 to 18 oxyethylene and / or oxypropylene groups, in the form of their sodium, potassium or alkanolamine salts,
• b) at least one nonionic surfactant,
• c) at least one alkaline salt,
• d) at least one sequestrant,
• e) optionally perfumes and / or dyes and / or other compatible additives, and
• f) water for the complement,

said composition comprising 4 - 8% of soaps and 11 - 26%, preferably approximately 16%, of phosphoric ester or of a mixture of phosphoric ester and at least one other anionic surfactant.

According to an advantageous embodiment, the composition according to the invention is concentrated and comprises from 30 to 60%, preferably 40 to 50%, of active material; the term active ingredient is understood to mean all the surfactants a) and b), alkaline salts c) and sequestering agents d).

• a) 15 - 30 %, de preférence 18 - 25 % et de façon encore plus préférée environ 20 %, d'agents de surface anioniques,
• b) 2 - 10 %, de préférence 4 - 8 %, d'agents de surface non ioniques,
• c) 5 - 15 %, de préférence 8 - 12 %, des sels alcalins
• d) 3 - 10 %, de préférence 3 - 8 %, de séquestrants, avec a + b + c + d = 30 - 60 %, ainsi que:
• e) éventuellement des parfums et/ou des colorants et/ou d'autres additifs compatibles, et
• f) de l'eau pour le complément.

Advantageously, the composition comprises:

• a) 15 - 30%, preferably 18 - 25% and even more preferably around 20%, of anionic surfactants,
• b) 2 - 10%, preferably 4 - 8%, of nonionic surfactants,
• c) 5 - 15%, preferably 8 - 12%, of the alkaline salts
• d) 3 - 10%, preferably 3 - 8%, of sequestrants, with a + b + c + d = 30 - 60%, as well as:
• e) optionally perfumes and / or dyes and / or other compatible additives, and
• f) water for the complement.

Preferably, the weight ratio between phosphoric ester and nonionic surfactants is 1.5 / 1 to 4/1, preferably 2/1 to 3/1. More particularly, for a phosphoric ester content of the composition of approximately 14%, the proportion of nonionic surfactants is preferably between 5 and 7%.

The weight ratio between the phosphoric ester and the other optional nonionic anionic surfactants is preferably from 1/1 to 20/1.

The composition advantageously constitutes a single stable phase. It is alkaline and in its preferred embodiments it has a pH of 10-11.

The individual components of the present cleaning compositions are described in detail below.

Anionic surfactants.

The anionic detergents which are used according to the invention comprise at least one soap and at least one oxyalkylenated phosphoric ester.

Among the natural soaps which can be used here, mention will be made of the sodium, potassium or alkanolamine salts of higher fatty acids, preferably containing from 12 to 20 carbon atoms, originating from plant or animal esters, for example example of palm oil, coconut oil, tallow or mixtures thereof. The potassium salts of a mixture of C ₁₂ to C _{18 '} fatty acids are preferred _.

In the oxyalkylenated phosphoric esters which are used according to the invention also called alkyl ether phosphates, the alkyl chain of the esterifying group comprises between 8 and 12 carbon atoms and the oxyalkylene or ether group comprises from 2 to 18 oxyethylene and / or oxypropylene groups , in the form of their sodium, potassium, or alkanolamine salts (mainly mono-, di- or tri-ethanolamine).

In the present context, the term phosphoric ester is understood to mean both the monoester and the diester or even, which is the preferred case since it corresponds to the formula of the commercial phosphoric esters, a mixture of the two.

These phosphoric esters are obtained, in known manner, by condensation reaction between oxyalkylated alcohols R (OC _x H _2x ) OH and a phosphoric or polyphosphoric acid, R being a C ₈ -C ₁₂ alkyl group, while x is equal to 2 or 3 and that y is a number from 2 to 18.

où R, x et y sont tels que définis ci-dessus, et où M est l'hydrogène, un cation alcalin choisi eutre sodium ou potassium, ou un reste d'alcanolamine.They can be represented by the formulas:

where R, x and y are as defined above, and where M is hydrogen, an alkaline cation chosen from sodium or potassium, or an alkanolamine residue.

• ^* Les agents de surface non ioniques.
• Parmi les agents de surface non ioniques qu'on peut utiliser selon l'invention, il convient de citer plus particulièrement les alcools gras oxyalkylénés et les alkylphénols oxyalkylénés, dont la chaîne alkyle comprend de 8 à 18 atomes de carbone et comportant de 4 à 18 groupes oxyde d'alkylène, de préférence en C₂-C₃.
• ^* Les sels alcalins.
• Ces composants correspondent aux adjuvants de détergence ou renforçateurs de détergence connus de l'homme du métier.
• Ce peuvent être de préférence des sels électrolytes alcalins, tels que des carbonates de sodium ou de potassium.
• ^* Les séquestrants.

Among the other anionic detergents which may also be present, if desired, in the composition according to the invention, mention may be made of alkylbenzene sulfonates having from 10 to 18 carbon atoms in the alkyl group, paraffin sulfonates having from 10 with 18 carbon atoms, the alpha-olefin sulfonates having from 10 to 18 carbon atoms, and the alkyl ether sulfates in which the alkyl group has from 10 to 16 carbon atoms and in which the ether group comprises between 2 and 6 alkylene oxide groups, preferably ethylene oxide. Among these optional additional compounds, the alpha-olefin sulfonates are preferred.

• ^* Non-ionic surfactants.
• Among the nonionic surfactants which can be used according to the invention, mention should be made more particularly of oxyalkylenated fatty alcohols and oxyalkylenated alkylphenols, the alkyl chain of which comprises from 8 to 18 carbon atoms and comprising from 4 to 18 alkylene oxide groups, preferably C ₂ -C ₃ .
• ^* Alkaline salts.
• These components correspond to detergency builders or detergency enhancers known to those skilled in the art.
• They can preferably be alkaline electrolyte salts, such as sodium or potassium carbonates.
• ^* The sequestrants.

• - les polyphosphates (pyro- ou tripoly-phosphates) de sodium ou de potassium,
• - les polycarboxylates, tels que l'éthylène diamine trétraacétate, le nitrilotriacétate et le citrate de sodium ou de potassium,
• - les polyphosphonates, tels que l'éthylène diamine tétraméthylène phosphonate et le diéthylène triamine pentaméthylène phosphonate de sodium ou de potassium.

Among the sequestrants known to a person skilled in the art which can be used according to the invention, particular mention should be made of:

• - sodium or potassium polyphosphates (pyro- or tripoly-phosphates),
• - polycarboxylates, such as ethylene diamine tretraacetate, nitrilotriacetate and sodium or potassium citrate,
• - polyphosphonates, such as ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate of sodium or potassium.

The composition according to the invention can also comprise, if desired, other non-essential constituents, such as perfumes and / or dyes and / or other compatible additives, intended to improve the properties or the aesthetic appeal. compositions.

The cleaning composition for hard surfaces according to the invention can be formulated by preparing each of its components separately, if necessary, and then mixing them thoroughly, together with the water which constitutes the solvent medium. This preparation can be done using techniques known to those skilled in the art.

In its concentrated embodiment, in particular with an active material content of 30 to 60%, the composition advantageously comprises, as component (f), deionized water or demineralized water. As a variant, the concentrated composition as above can be diluted, either from its manufacture, or before use, and stored in this diluted form. In this case, the complementary water can be, for all or part, tap water.

The composition obtained both in its concentrated variant and in its diluted variant, and in particular that which comprises the preferred components indicated above and whose respective proportions of the components are those indicated above with reference to the concentrated formula, is stable on storage. , advantageously in a single clear phase.

It has been unexpectedly found that the composition in concentrated form according to the invention can very well be diluted, in particular before being used or before being stored by the end user, for example according to a dilution causing the volume to pass. from 1 to 4 approximately, simply by adding to the initial volume of concentrated composition the appropriate volume of tap water, whatever the temperature and the hardness thereof, and then a dilute, clear and liquid composition is obtained. stable without flocculation, in particular with the preferred components indicated above and with the respective proportions of the components indicated above with reference to the concentrated formula.

The diluted composition obtained also forms part of the present invention. It constitutes a product corresponding to household habits and to a rate of active cleaning material suitable for the cleaning to be performed, in particular for cleaning, both occasional and routine, of hard floors, tiles, washable painted surfaces, floor plans. work, sanitary appliances, etc.

The primary advantage of the concentrated formulation over this diluted formulation is that, while allowing the end user to easily obtain it and store it for later uses, it makes possible a clear reduction in costs and constraints. of demineralization of tap water for the industrial manufacturer and makes it possible to considerably reduce the weight and volume of the packaging, as well as the storage and transport costs, for an equivalent content of active material.

Used under normal conditions and according to current household habits, the compositions according to the invention ensure the elimination of all stains, even very stubborn, on hard surfaces both slightly porous and non-porous, and dry without traces.

In the compositions according to the invention, the soap makes an essential contribution to the detergent power on hard surfaces and, in combination with the phosphoric esters and the nonionic surfactants, it ensures the stability of the composition in a single and clear liquid phase. .

The invention is illustrated in more detail in the examples below, which do not limit it in any way. In these examples also; the percentage indications are understood to be by weight of the 100% pure component, relative to the total weight of the composition. The abbreviations used, for example C _t pC _t4 , 5 EO, are conventional and define on the one hand the number of carbon atoms of the alkyl groups and on the other hand the contents in ethylene oxide groups of the molecules concerned.

Example 1.

Eight cleaning compositions for hard surfaces were prepared, the components and their weight proportions of which are indicated in Table 1 below (compositions Nos. 1 to 8).

Composition No. 1 was prepared as follows: in 530 g of C ₈ alkyl ether phosphate, 6 EO at 30%, neutralized with triethanolamine and stirred with 110 g of deionized water, 7 g of potassium hydroxide were dissolved and neutralized with 35 g of fatty acids; 160 g of 50% potassium carbonate and 80 g of trisodium citrate dihydrate were added. Stirring was continued until the solids were completely dissolved, then 80 g of C ₁₂ -C ₁₄ oxyethylenated fatty alcohol, 7 EO were added and the mixture was stirred for approximately 15 to 30 minutes.

To prepare compositions no. 2 to 8, the same procedure was used, but each time replacing the above-mentioned phosphoric ester with that indicated in table 1 in each case.

The comparison of these compositions highlights the influence of the length of the alkyl ether phosphate alkyl chain on the characteristics of the corresponding compositions; thus:

Composition No. 1 formed a single, clear phase; it had a cloud point of 92 ° C and a viscosity of 62 mPa.s. Dilution of this composition up to 4 times its initial volume gave a slight precipitate if it was made with tap water, and a solution in a single phase always perfectly clear when it was made with deionized water .

Compositions 2, 3, 4, 6, 7 and 8 gave two phases; composition No. 7 also gave rise to a slight precipitation of a solid.

Composition No. 5 formed a unique, clear phase; it had a cloud point of 58 ° C and a viscosity of 326 mPa.s. Dilution of this composition up to 4 times its initial volume gave a slight precipitate if it was made with tap water and a solution in a single phase always perfectly clear when it was made with deionized water.

Example 2.

Five other cleaning compositions for hard surfaces in accordance with the invention were prepared, having the respective components and the weight proportions indicated in Table II below (compositions Nos. 9 to 13).

Composition No. 9 was prepared as follows in 466 g of alkyl ether phosphate C ₈ , 6 EO at 30%, neutralized with triethanolamine and stirred with 12 g of deionized water, 52 g of was added. 38.5% sodium alphaolefin sulfonate. Once the stirred medium was clear, 7 g of potassium hydroxide were dissolved therein and neutralized with 35 g of fatty acids; 160 g of 50% potassium carbonate and 19 g of 37.5% EDTA were then added. Stirring was continued until the solids were completely dissolved, then 80 g of C ₁₂ -C ₁₄ oxyethylenated fatty alcohol, 7 EO were added and the mixture was stirred for approximately 15 to 30 minutes.

To prepare compositions no. 10 to 13, the procedure was the same, but by varying the proportions of the constituents as indicated in table II.

Table II also groups together the indications concerning the physical state, the cloud point and the viscosity of the compositions, as well as the physical state of the compositions after dilution of the concentrated composition concerned up to 4 times its initial volume of water. tap.

The comparison of these compositions shows the influence of the alkyl ether phosphate / sulfonate ratio on physical stability.

Example 3.

By operating as for composition No. 5 of Example 1, but replacing the citrate with an equivalent amount of sodium nitrilotriacetate, a composition (No. 14) according to the invention was obtained having the characteristics indicated below. below.

The clear dilute formulations of the above examples were tested for gloss on shiny and colored ceramics and for removing stains (fats, street dust and smoke black) on plastic surface and on matt ceramic.

The results obtained make it possible to consider that the compositions tested are at least equivalent to the commercial products currently on the market for cleaning hard surfaces, both for the gloss criterion and for that of detergency.

Claims (6)

1. An alkaline liquid composition that can be diluted with water, for the cleaning of hard surfaces, characterized in that it contains:

a) at least two anionic surface agents, including at least one soap and at least one phosphoric ester chosen from the oxyalkylene phosphoric esters or alkyl ether phosphates in which the alkyl chain of the esterification grouping comprises between 8 and 12 carbon atoms, and the oxyalkylene or ether grouping comprises from 2 to 18 oxyethylene and/or oxypropylene groups in the form of their sodium, potassium or alcanolamine salts,

b) at least one non-ionic surface agent,

c) at least one alkaline salt,

d) at least one sequestering agent

e) possibly perfumes and/or colouring agents and/or other compatible additions, and

f) water to make up the desired quantity,
the said composition comprising 4 - 8 % of soaps and 11 - 26 %, preferably about 16 %, of phosphoric ester or of a mixture of phosphoric ester with at least one other anionic surface agent.

2. A composition according to Claim 1, characterized in that the proportion of (a) is 15 - 30 %, preferably 18 - 25 %, the proportion of (b) is 2 - 10 %, preferably 4 - 8 %, the proportion of (c) is 5 - 15 %, preferably 8 - 12 %, and the proportion of (d) is 3 - 10 %, preferably 3 - 8 %.

3. A composition according to one of Claims 1 and 2, characterized in that the weight ratio between the phosphoric ester and the non-ionic surface agents is from 1.5 : 1 to 4 : 1, and the weight ratio between the phosphoric ester and the other anionic surface agents that are not soaps, if there are any, is from 1 : 1 to 20 : 1.

4. A composition according to Claim 1, characterized in that it is in the form of a single-phase liquid composition.

5. A composition according to Claim 1, characterized in that it is modified by dilution, preferably by a dilution that increases the volume from 1 to approximately 4, with tap water as all or part of the added water.

6. The use of an alkaline liquid composition to clean hard surfaces according to Claim 1, characterized in that it includes the dilution of the said composition in which the total of constituents (a) to (d) represents 30 to 60 % of the total weight of the composition.