WO2017009561A1 - Cleaning composition - Google Patents

Abstract

A microemulsion cleaning composition comprising: a) an oil comprising terpinolene and/or a fatty acid ester, b) a sorbitan-derived polyethoxylated surfactant, c) a polyethoxylated polypropoxylated terpene co-surfactant, d) optionally a hydrotrope such as ethanol, and e) water. The invention also relates to a process for producing the microemulsion and also to the use thereof for cleaning.

Description

 Cleansing Composition

Field of the invention

 The invention relates to a cleaning composition, preferably in microemulsion form, having a good biodegradability, which is dilutable and effective for cleaning surfaces (metals, plastics, fibers, sand, etc.) soiled by various organic fouling (bitumens). vegetable oils, paraffinic oils, lanolin, etc.).

 Prior art

 Most cleaning products used contain volatile organic compounds (VOCs) that are toxic to humans and harmful to the environment. They are generally not very biodegradable. In addition, the commonly used solvents (glycol ethers, aromatic solvents, ketones) often have a low flash point and are therefore highly flammable. Although effective and versatile, such compositions are undesirable because of the risks they pose to human health and the environment. In addition, these products are formulated based on petrochemical compounds and therefore have a non-renewable nature.

 Alternatives currently on the market may be products based on agro-sourced solvents or aqueous compositions. The formulas based on bio-solvents are effective but do not solve the problems of flammability and volatility. The water-based products have a reduced flashpoint and low volatility but are not necessarily biodegradable and are frequently at a high pH which induces corrosion of some surfaces and poses a risk to the operators. In addition, the aqueous formulations are not always dilutable and when they are, there is a decrease in cleaning efficiency when the water content is high. In addition, the aqueous products are often in the form of emulsions and are therefore turbid and may be unstable on storage.

It has already been proposed in patent applications WO 2012/071059 "Dilutable cleaning compositions and methods for use" and WO 2012/078193 "Dibasic esters used as terpene co-solvents, substitutes and / or carriers tar sand / bitumen / asphalten cleaning applications "ecological cleaning compositions comprising a low VOC content. However, there remains a need for cleaning formulations with a good HSE profile (better biodegradability, low toxicity, low volatility, low flammability, stable and dilutable microemulsion) and which have an efficiency for a wide range of soils and especially heavy oils, which are particularly difficult to clean. The invention therefore proposes a composition, in particular in the form of a microemulsion, responding to at least one, and preferably all, of the following problems:

 - Environment: better biodegradability, low toxicity and agro-sourced origin of some of the components

 - Safety: low volatility, low flammability and neutrality of the formulation

- Efficiency: clear, stable and effective formula including high dilution rate for various soils and reputed to be difficult to clean (oil, wool fat, vegetable oils and fats, mineral greases, etc.).

 A microemulsion is a thermodynamically stable dispersion of two immiscible liquids, stabilized by a surfactant. These dispersions are generally transparent because the typical mesophase sizes are smaller than the wavelength of the light, and often nanometric.

 A stable microemulsion according to the invention is advantageously a microemulsion which remains visually monophasic more than 7 days, preferably more than 30 days, and even more preferably, more than 365 days, under normal conditions of temperature and pressure. Advantageously, a stable microemulsion also remains translucent under the same conditions as indicated above.

 Description of the invention

 An object of the invention is a microemulsion, preferably based on water, comprising or consisting of:

 a) an oil comprising or consisting of terpinolene and / or a fatty acid ester (for example methyl oleate and / or isoamyl laurate),

 b) a polyethoxylated surfactant derived from sorbitan,

 c) a polypropoxylated polyethoxylated terpene co-surfactant,

 d) optionally a hydrotrope such as ethanol, and

 e) water.

 It should be noted that these constituents may be directly derived or derived from agro-resources. The cleaning / degreasing efficiency of the mixture has been proven on various soils.

 The fatty acid ester may be a natural fatty acid ester having a carbon chain of 4 to 36 carbon atoms or a mixture of such fatty acid esters. Preferably it is either methyl oleate or isoamyl laurate, or a mixture of these compounds.

 The polyethoxylated surfactant derived from sorbitan is preferably selected from the group of fatty acid esters such as:

polysorbate 20: polyethoxylated sorbitan monolaurate (20EO) (CAS No. 9005- 64- 5);

 polysorbate 40: polyethoxylated sorbitan monopalmitate (20EO) (No.

 CAS9005-66-7);

 polysorbate 60: polyethoxylated sorbitan monostearate (20EO) (CAS No. 9005-67-8); and

 polysorbate 80: polyethoxylated sorbitan monooleate (20EO) (CAS No. 9005-

65-6); as well as their mixtures.

 Among these compounds, polysorbate 20 and polysorbate 80 are particularly preferred. Also, the polyethoxylated surfactant derived from sorbitan advantageously comprises polysorbate 20 and / or polysorbate 80.

The polyethoxylated polypropoxylated terpene co-surfactant is preferably a copolymer block of which the terpene group corresponds to nopol, or polyethoxy-polypropoxenopol (CAS-No .: 174955-61-4).

 The hydrotrope is advantageously chosen from known short amphiphilic polar solvents. Ethanol is particularly preferred.

 According to a first variant of the invention, the microemulsion comprises a hydrotrope and preferably ethanol.

 It has been found that the combination surfactant, co-surfactant, hydrotrope in respective proportions by weight of 1: 6: 1, makes it possible to obtain a microemulsion and also makes it possible to avoid any phenomenon of structuring of the medium which results in a high viscosity less compatible with the degreasing application. It has indeed been observed that a too small or too high amount of surfactant leads to an unstable emulsion or to formulations that are not very dilutable. In addition, an insufficient amount of co-surfactant can lead to an unstable or little-dilutable emulsion, whereas a too large quantity considerably reduces the cleaning / degreasing efficiency of the formula. Finally, a too small amount of hydrotrope causes the appearance of liquid crystals making the composition very viscous and less effective for degreasing, too much leads to an unstable emulsion or formulas with little or no dilution.

Thus, surprisingly, a synergy has been detected between these three constituents which allows both the easy formation of a microemulsion and the obtaining of a higher degreasing efficiency for specific relative mass proportions. An object of the invention is therefore a microemulsion whose mass proportions between the surfactant, the co-surfactant and the hydrotrope have a ratio of 1: 6: 1. Each of these 1: 6: 1 ratios can vary from each other by about 20% or about, preferably less than 10%, and more particularly about 5% without the synergistic effect being significantly affected. Depending on the amount of water used, this microemulsion may be a water-in-oil (w / o) or oil-in-water (o / w) microemulsion.

 Mass proportions between surfactant, co-surfactant and hydrotrope of ratio 5: 10: 3 and 1: 4: 1 also showed satisfactory results.

 According to a preferred aspect of the first variant of the invention the microemulsion comprises, or consists of:

a) terpinolene and / or a fatty acid ester (for example methyl oleate and isoamyl laurate),

b) polysorbate 20 or 80,

(c) Polyethoxypropoxy-nopol (CAS No: 174955-61-4),

(d) ethanol, and

e) water.

 Terpinolene and the fatty acid ester (for example methyl oleate and isoamyl laurate) are oils which can act as a solvent. In general, terpinolene is preferred for soils of the "mineral" type and a fatty acid ester for soiling of the "plant" type.

 In addition, the presence of terpinolene makes it possible to obtain a microemulsion which can be diluted with water in large proportions without losing its properties. Thus a microemulsion according to the invention is a particularly adaptable composition since very highly dilutable. A microemulsion diluted to 80% water is effective for degreasing is part of the invention.

 It has also been found that a mass ratio between the surfactant, cosurfactant and hydrotropic mixture on the one hand, and the oil on the other hand, of 80:20 makes it possible to obtain compositions which can be highly diluted.

 The microemulsion can be enriched in oil (for example up to 60% by weight) for the cleaning of greasy vegetable soils.

 Also a particularly preferred microemulsion according to the invention comprises, or consists of,

 a) terpinolene,

 b) polysorbate 20,

 (c) polyethoxypropoxy-nopol (CAS No: 174955-61-4),

 (d) ethanol, and

 e) water.

 In a still more preferred aspect, the relative proportions by weight of b / c / d (or polysorbate 20 / polyethoxypropoxy-nopro / ethanol) are 1: 6: 1.

Another particularly preferred microemulsion comprises, or consists of from:

 a) methyl oleate

 b) polysorbate 80,

 (c) polyethoxypropoxy-nopol (CAS No: 174955-61-4),

 (d) ethanol, and

 e) water.

 According to an even more preferred aspect, the relative proportions by weight of b / c / d (or polysorbate 80 / polyethoxypropoxy-nopol / ethanol) are 1: 6: 1.

 A particularly preferred microemulsion formulation is a microemulsion comprising, or consisting of:

 a) at least 4% by mass of terpinolene, preferably at least 6% and advantageously at least 8%,

 b) from 3 to 6% by weight of polysorbate 20, preferably 4%,

 c) from 22 to 26% by weight of polyethoxypropoxy-nopol, preferably 24% d) from 3 to 6% by weight of ethanol, preferably 4%, and

 e) 56 to 66% water, preferably 60%.

 Such a microemulsion is particularly stable and can clean a range of soils particularly varied.

 According to a second preferred variant of the invention, the microemulsion comprises, or consists of,

 - isoamyl laurate,

 - methyl oleate,

 - a mixture:

 from 70 to 95% by weight of 2-methyl dimethylglutarate (CAS: 14035-94-0),

 from 5 to 30% by weight of dimethyl ethylsuccinate (CAS: 14035-95-1), and

 0 to 10% by weight of dimethyl adipate (CAS No .: 627-93-0),

terpinolene,

polyethoxypropoxy-nopol (CAS No. 174955-61-4),

 polysorbate 20,

 - (3R) -3-ethoxy-2-methylnonane (CAS No. 78330-20-8), and

 - some water.

 According to this second preferred variant of the invention the mass proportion of the isoamyl laurate is advantageously greater than 14%, preferably about 17% ± 1, for example 6.81%.

The mass proportion of methyl oleate is preferably about 2% ± 1, by example 2.2%.

 The mass proportion of the mixture of:

 - from 70 to 95% by weight of 2-methyl dimethyl glutarate (CAS: 14035-94-

0)

 from 5 to 30% by weight of dimethyl ethylsuccinate (CAS: 14035-95-1), and

from 0 to 10% by weight of dimethyl adipate (CAS No. 627-93-0);

 is preferably about 10% ± 5%, preferably 10% ± 1, for example 10.23%.

 According to one embodiment, this mixture contains dimethyl adipate at a content of less than 10% by weight, preferably less than 5% by weight.

 The amount of terpinolene is preferably at least 0.5% by weight, preferably about 1% ± 0.2, for example 1.3%.

 The amount of polyethoxypropoxy-nopol is preferably not greater than 1.2% by weight, preferably about 0.7% ± 0.2, for example 0.71%.

The amount of polysorbate 20 is preferably about 0.8% ± 0.2 by weight, for example 0.71%.

 The amount of (3R) -3-ethoxy-2-methylnonane is advantageously less than 60% by weight, preferably about 55% ± 3%, for example 56.91%.

The amount of water is preferably 5% ± 1 by mass.

Preferably, when the microemulsion according to the variants of the invention consists of the ingredients mentioned above, the water is added in sufficient quantity to reach 100% by weight.

 Advantageously, a microemulsion according to the second variant of the invention may be diluted with water. For example the amount of water can be 60% by weight. In this case, a microemulsion according to the invention which is particularly preferred has the following mass proportions:

 isoamyl laurate is advantageously greater than 7%, and preferably about 7.5% ± 1, for example 7.56%.

 The mass proportion of methyl oleate is preferably about 1% ± 0.1, for example 0.99%.

 The mass proportion of the mixture of:

 - from 70 to 95% by weight of 2-methyl dimethyl glutarate (CAS: 14035-94-

0)

 from 5 to 30% by weight of dimethyl ethylsuccinate (CAS: 14035-95-1), and from 0 to 10% by weight of dimethyl adipate (CAS No. 627-93-0);

is preferably about 5% ± 1, preferably 4.5% ± 0.5%, for example The amount of terpinolene is preferably at least 0.5% by weight, preferably about 0.59% ± 0.1, for example 0.59%.

 The amount of polyethoxy-polypropoxy-nopol is preferably not greater than 1% by weight, preferably it is about 0.35% ± 0.3, for example 0.32%.

 The amount of polysorbate 20 is preferably about 0.3% ± 0.2 by weight, for example 0.32%.

 The amount of (3R) -3-ethoxy-2-methylnonane is preferably less than 27% by weight, preferably about 25% ± 1, for example 25.6%.

 The amount of water is preferably about 60% ± 1 by weight. However, it should be noted that dilution with water only slightly affects the cleaning power of this microemulsion.

The microemulsion according to the invention is therefore a composition comprising water. However, the base compositions, or "concentrated", comprising all the ingredients with the exception of water and making it possible to obtain the microemulsions also form part of the invention. Thus, such a base composition can comprise, in weight percentage, 20% of oil (for example terpinolene), 10% of polyethoxylated surfactant derived from sorbitan (for example from polysorbate 20), 60% of polyethoxylated terpene polypropoxylated co-surfactant ( for example polyethoxypropoxy-nopol) and 10% hydrotrope (for example ethanol).

Another aspect of the invention is a method of manufacturing the microemulsions or base compositions according to the invention comprising a step of mixing the ingredients constituting these compositions (that is to say microemulsions or base compositions). Thus, this process may comprise at least one step of mixing the oil, the polyethoxylated surfactant derived from sorbitan and the polyethoxylated polypropoxylated terpene co-surfactant followed by the addition of water with stirring.

 Preferably, for the manufacture of a composition according to the first variant of the invention, the process is carried out by adding and mixing the surfactant and co-surfactant with the oil (solvent), and then mixing the hydrotrope with mixture obtained. The water is then optionally added and mixed with this medium. Preferably, the temperature of the water when it is added is greater than or equal to 15 ° C.

For the manufacture of a composition according to the second variant of the invention the ingredients of the composition are mixed with each other in the following order:

- isoamyl laurate,

- Rhodiasolv Iris, methyl oleate,

 terpinolene 95PF,

 - Rhodoclean MSC,

 - Radiasurf 7137,

 - Rhodasurf Da / 630-E, and possibly

 - water.

 Another aspect of the invention is the use of a microemulsion according to the invention for the cleaning, industrial or otherwise, of surfaces, textiles, fibers, sand or various materials such as metals or plastics. In particular, a microemulsion according to the invention can be used for the cleaning of petroleum stains and its derivatives (for example, tars, bitumens, hydrocarbons, paraffinic oils, lanolin), a heavy oil, a grease or fats. vegetable or animal oil (eg, wool fat) and / or mechanical lubricant (e.g., motor oil), etc.

 The term "cleaning" includes the degreasing and / or decontamination of a substrate.

 Another aspect of the invention is the use of the base compositions, or concentrates, according to the invention, in the manufacture of microemulsions. Thus, the invention also relates to a cleaning composition without water, as well as to its method of manufacture. Such compositions may advantageously be mixed with water to obtain cleaning compositions and more particularly, after stirring, microemulsions according to the invention. The percentages by weight are measured with respect to the total mass of the composition. The invention will be better understood on reading the appended figures, which are provided by way of examples and are in no way limiting, in which:

 Figure 1 is a photograph illustrating the effectiveness of cleaning microemulsions 1D and V1 to V7 on a heavy oil soiled plate.

 Figure 2 is a photograph illustrating the effectiveness of cleaning microemulsions T and M1 to M4 on a heavy oil soiled plate.

In the following examples commercially available ingredients have been used. It is :

 - Rhodasurf DA630 E ™: (Ethoxylated ester) product sold by Rhodia.

 IUPAC (3R) -3-ethoxy-2-methylnonane. CAS-No .: 78330-20-8. Gross formula: C12H260

- Rhodiasolv IRIS ™ (IRIS) product sold by Rhodia: Mixture mass percentages of:

 from 70 to 95% by weight of 2-methyl dimethylglutarate (CAS: 14035-94-0),

 from 5 to 30% by weight of dimethyl ethylsuccinate (CAS: 14035-95-1), and

 0 to 10% by weight of dimethyl adipate (CAS No .: 627-93-0),

Rhodoclean MSC ™, product sold by Rhodia: Aqueous solution (50% by weight) of a mixture based on ethoxylated-propoxylated terpene (copolymer block) or nopol ethoxylated propoxylated or polyethoxy-polypropoxenopol (CAS No. : 174955-61 -4).

 Radiasurf 7137 ™ (polysorbate 20) product sold by OLEON: polyethoxylated sorbitan monolaurate (20EO) (CAS No. 9005-64-5).

 Radiasurf 7157 ™: (polysorbate 80) product sold by the company Oleon: polyethoxylated sorbitan monooleate (20EO) (CAS No. 9005-65-6).

 Terpinolene 95PF ™: isoterpinene (CAS No. 586-62-9) or 1-methyl-4- (prop-1-en-2-yl) cyclohex-1-ene.

A. Example 1 A concentrated composition 1 (Formula 1) according to the invention is prepared at room temperature (18/23 ° C.) according to the following procedure:

 -In a clean 250ml beaker kept under continuous stirring (there should be a slight vortex formation), add 8gr terpinolene 95PF.

 -See 4gr of Radiasurf 7137 in the beaker. Stir about 1 min.

 -Take 24g of Rhodoclean MSC distilled (water content <1%) into the beaker. Shake 5min.

 -Pour 4 g of ethanol (purity> 96%) into the beaker. Shake 5min. A concentrated or basic composition of formula 1 is obtained.

The proposed compositions are adaptable. For example, the microemulsion of Formula 1 is infinitely dilutable. By diluting Formula 1 to 80% water, Formula B is also effective for degreasing.

Microemulsions 1A and 1B are obtained by slowly pouring 11, 11 g (1A) or 400 g (1 B) gr of tap water at room temperature into the beaker. The compositions are stirred vigorously for 5 to 10 minutes until a complete homogeneity and a microemulsion are obtained. Formula 1 can be enriched with terpinolene (60% by weight for example) to obtain the formula 1C useful for the most difficult to remove dirt. A 1C composition is obtained using the procedure described above but using different proportions of components so as to obtain the composition as described in Table I.

The compositions of formulas 1, 1A, 1B, 1C and 1D are as follows: TABLE I

 Molecules Formula 1 Formula 1A Formula 1 B Formula 1C Formula 1D

 (T)

Water / 10% 80% 8% 60%

Terpinolene 20% 18% 4% 60% 8%

Radiasurf 7137 10% 9% 2% 4% 4%

Rhodoclean MSC 60% 54% 12% 24% 24%

Ethanol 10% 9% 2% 4% 4%

wt%

Comparative tests of degreasing efficiency

 These tests were conducted using various commonly used cleaning products and their results are compiled in Table II.

The DET 1003 product is a "universal" aqueous alkaline detergent sold by Chimie Recherche Environnement Evolution (CREE). It contains dissolved alkaline mineral salts, glycol ether, a sequestering agent, and a nonionic surfactant and is pH13.

The product CREEDO Remover is a solvent mixture comprising a base of esters, plant extracts and a nonionic surfactant, which is sold by CREE. TABLE II

 Degreasing efficiency (%)

 Degreasing product Grease Fat

 Oil

of food wool ⁹

CREEDO 13 42 81

DET 1003 11 11 21

Formula 1A 86 77 37

 Formula 1 B (i.e. formula 1 diluted at 80%

 47 52 100 in water)

 Formula 1 C (i.e. formula 1 concentrated at

 100 100 41 60% terpinolene)

 a) the dietary fat mixture is composed of 45% water, 17% flour, 5% milk powder, 4.8% beef fat, 4.8% butter, 4.8% butter olive oil, 4.8% sunflower oil, 4.8% lard, 4.8% margarine, 4% cream and 0.2% dye.

The microemulsions according to the invention remain capable of cleaning / degreasing soils reputed to be difficult to remove (oil and wool fat), for high water contents. The formulas according to the invention are more effective than commercial products, even when they are very dilute. The ability to concentrate in a solvent increases efficiency if high performance cleaning is required.

Effect of variation in proportions of compounds (except water).

The effect of varying the relative proportions of the components and in particular the surfactant / co-surfactant / hydrotrope is important for optimizing the composition. Thus, compositions V1 to V7 exhibiting variations in the surfactant, co-surfactant, hydrotrope and oil proportions were produced and tested. A reference composition 1D (composition 1 diluted to 60% water) is used. Table III shows the mass proportions of the compositions.

 TABLE III

 1D VI V2 V3 V4 V5 V6 V7

Terpinolène 95PF 8 4 8 8 8 8 8 8 adiasurf 7137 4 4 2 8 4 4 4 4

Rhodoclean MSC 24 24 24 24 20 28 24 24

Ethanol 4 4 4 4 4 4 2 8

Water 60 64 62 56 64 56 62 56 These compositions are prepared according to the procedure described above.

 In formulas V2, V4, V6 and V7, changes in the proportions of raw materials destabilize the microemulsion, making it cloudy at first and then causing it to shift later. Formula V3 is slightly cloudy but remains stable. The other formulas are not destabilized.

 An efficiency test is then carried out on a support soiled with a heavy oil residue (bottom of tank). This test is carried out using brushes soaked with the microemulsion according to the invention and formulas V1 to V7. Figure 1 is a photograph of the result of these tests. The position of the test carried out with the microemulsion 1D is identified as "T" and the positions of the tests carried out using the formulas V1 to V7 as 1 to 7.

 A substantial difference in effectiveness between the different formulas is established. As is apparent in Figure 1, there is a very significant loss of efficiency when changing the proportions of some of the ingredients used.

B. Example 2

A concentrated composition 2A according to the invention is prepared at ambient temperature (18/23 ° C.) according to the following procedure:

To prepare 50 g of microemulsion, 2 g of Radiasurf 7157, 2 g of ethanol and 12 g of Rhodoclean MSC (distilled, water content of less than 1%) are introduced in this order in a 125 ml flask at bottom. dish equipped with a magnetic bar. 30 g of methyl oleate are added and the system is stirred slowly (250 rpm) at room temperature until complete dissolution (1 minute). While maintaining the stirring, 4 g of demineralized water are introduced. Stirring is stopped when the medium is completely homogeneous (transparent and fluid). This particular microemulsion tolerates a large variation in the oil content (methyl oleate). C. Comparative efficacy test

The formulas tested are the compositions 1A and 2A previously described, the formulas of which are summarized in Table IV: Table IV

 Content (% by mass)

 Components Microemulsion Microemulsion Function

 Formula 1A Formula 2A

Phase

 Water 10 8

 aqueous

 Terpinolene Oil 18 -

Methyl Oleate Oil - 60

 Radiasurf 7137 Surfactant 9 -

Radiasurf 7157 Surfactant - 4

 Rhodoclean MSC Co-surfactant 54 24

 Ethanol Hydrotrope 9 4

The effectiveness of these microemulsions of Formula 1A and 2A has been tested on several soils as compared to commercial reference products: DIESTONE DLS (solvent mixture sold by Socomore containing ketones and petroleum distillates) and DET 1003 ( see above).

The performance test is performed by dipping a metal plate covered with a dirt film into a beaker filled with the product to be tested. The dirt film is a mechanical lubricant (Renolit CAN 2 from the company FUCHS) or a SPIREL brand vegetable fat. After stirring for 30 minutes (magnetic bar), the plate is removed from the bath and the efficiency is calculated using the ratio of the soil mass removed on the initial soil mass. The results are shown in Table V below.

 Table V

 Degreasing efficiency (%)

 Grease Lubricant

 Degreasing product

 vegetable mineral

 (Fuchs) (Spirel)

 Diestone DLS 18 51

 DET 1003 76 100

 Formula 1A 93 /

 Formula 2A / 99

During the degreasing of a metal plate soiled by a mechanical lubricant (Renolit CAN2, Fuchs) using the microemulsion of formula 1A, a cleaning effect by tearing of soil flaps and solubilization is observed between 300 and 340 seconds. It contributes to the effectiveness of microemulsions.

 The effectiveness of the diluted formulas 1A and 1B, as well as the intermediate dilution formulas obtained according to the protocol previously described, was also tested according to the same protocol, with respect to the mineral fouling (lubricant Fuchs). The results are shown in Table VI below:

 Table VI

 Water content

Degreasing product Degreasing efficiency {% ₁

 % mass

 Formula 1A 10 93

 Formula 30 30 92

 Form 45 45 99

 Formula 60 60 96

 Formula 1B 80 76

D. Example 3

A concentrated composition 3 (Formula 3) according to the invention is prepared at ambient temperature at a temperature above 20 ° C. according to the following procedure: In a clean beaker of 250 ml maintained under continuous stirring (there must be formation of a slight vortex),

 - add 7.56 g of isoamyl laurate.

 -See 4.6gr of Rhodiasolv Iris in the beaker. Shake 1 min.

 - Pour 0.99gr of methyl oleate into the beaker. Shake 1 min.

-See 0.59gr of Terpinolene 95PF in the beaker. Shake 1 min.

-See 0.32gr of Rhodoclean MSC ^* into the beaker. Shake 5min.

 -See 0.32gr of Radiasurf 7137 in the beaker. Shake 5min.

 -See 25.6gr of Rhodasurf Da / 630-E in the beaker. Disperse quickly for 15min.

-See 5gr of tap water into the beaker. Shake 15min.

 In this example, Rhodoclean MSC is used in its commercial formulation, that is, it contains 50% water. In the previous examples it was used pure.

Concentrated Formula 3 or base composition is obtained. This can be diluted up to 60% by weight of water. To obtain the ready-to-use microemulsion T:

-Slowly pour 55g of tap water into the beaker. The water temperature must not be lower than 15 ° C. Shake 15min.

-If the mixture is not clear, warming the solution with a slight increase in temperature between 20 and 25 ° C can remove the haze and obtain a microemulsion stable storage,

- let stand for 30 min. Effect of variation of the proportions of the compounds.

The formulation T can be diluted with water, for example up to 60% water by weight.

 The variation of the relative proportions of the other components of the formulation 3, or T, important can lead to less efficient microemulsions. Thus, compositions M1 to M4 with variations in surfactant / cosurfactant / hydrotrope proportions were made and tested. A reference composition T (the composition 3 diluted with 60% water) is used. Table VII shows the mass proportions of the compositions.

TABLE VII

These compositions are prepared according to the procedure described above in Example 3.

Microemulsion T

Formula M1: Decrease of 2% of isoamyl laurate.

M2 formula: 0.5% increase in Rhodoclean MSC.

Formula M3: 5% increase in Rhodasurf DA / 630-E.

Formula M4: Decrease of 0.5% Terpinolene 95PF. An efficiency test is then carried out on a support soiled with a heavy oil residue (bottom of tank). This test is performed using brushes soaked in different formulas that are applied to different sections of the same support. The sections T, 1, 2, 3 and 4 of FIG. 5 respectively correspond to the application of the formulas T, M1, M2, M3 and M4. As is apparent in Figure 5, there is a very significant loss of efficiency when changing the proportions of some of the ingredients used.

 The invention is not limited to the embodiments presented and other embodiments will become apparent to those skilled in the art. Thus terpinolene could be replaced in whole or in part by a monoterpene linear, monocyclic or bicyclic, such as alphapinene or gasoline turpentine.

Claims

 1. Microemulsion comprising:  a) an oil comprising terpinolene and / or a fatty acid ester,  b) a polyethoxylated surfactant derived from sorbitan,  c) a polypropoxylated polyethoxylated terpene co-surfactant,  d) optionally a hydrotrope such as ethanol, and  e) water. 2. Microemulsion according to claim 1, characterized in that the fatty acid ester is either methyl oleate or isoamyl laurate, or a mixture of these compounds. 3. Microemulsion according to claim 1 or 2, characterized in that the polyethoxylated surfactant derived from sorbitan comprises polysorbate 20 and / or polysorbate 80. 4. Microemulsion according to any one of claims 1 to 3, characterized in that the polypropoxylated polyethoxylated terpene co-surfactant is polyethoxypropoxy-nopol. 5. Microemulsion according to claim 1, comprising a hydrotrope and preferably ethanol. 6. Microemulsion according to claim 5, characterized in that the mass proportions between the surfactant, the co-surfactant and the hydrotrope have a ratio of 1: 6: 1, each of these proportions being able to vary with respect to another 20%. 7. Microemulsion according to claim 5 or claim 6, characterized in that it comprises:  a) at least 6% by mass of terpinolene,  b) from 3 to 6% by weight of polysorbate 20,  (c) from 22 to 26% by weight of polyethoxypropoxy-nopol,  d) from 3 to 6% by weight of ethanol, and  e) 56 to 66% water. 8. Microemulsion according to any one of claims 1 to 4, characterized in that it comprises: isoamyl laurate; - methyl oleate;  - a mix of :  from 70 to 95% by weight of 2-methyl dimethyl glutarate, from 5 to 30% by weight of dimethyl ethylsuccinate, and  from 0 to 10% by weight of dimethyl adipate;  terpinolene;  polyethoxy-polypropoxynopol;  polysorbate 20;  (3R) -3-ethoxy-2-methylnonane; and  - some water. A process for manufacturing microemulsions according to any one of claims 1 to 8, comprising at least one step of mixing the oil, the polyethoxylated surfactant derived from sorbitan and the polypropoxylated polyethoxylated terpene co-surfactant, followed by an addition water with stirring. 10. Use of a microemulsion according to any one of claims 1 to 8 for the cleaning, industrial or otherwise, of surfaces, textiles, fibers, sand or materials such as metals or plastics for cleaning fouling of petroleum and its derivatives, eg tars, bitumens, hydrocarbons, paraffinic oils, lanolin, heavy oil, vegetable or animal fat or oil, eg wool fat and / or d a mechanical lubricant for example, motor oil.