EP1987125B1 - Liquid detergent composition containing an enzyme - Google Patents

Description

Object of the invention

The present invention relates to a liquid detergent composition obtained from renewable raw materials and comprising an enzyme. The detergent composition is for use in domestic and industrial applications.

Technological background

Cleansing and cleaning products containing enzymes are known and used in household applications, mainly in laundry and dishwashing applications, and in industry, for example food industries, for floors, walls and the home. cleaning in place. In products for domestic use, however, the use of enzymes is less common. Indeed, the addition of enzymes increases the cost of these products. It also requires know-how, especially to prevent any risk of allergy. It is known that the addition of enzymes to a liquid detergent composition rapidly degrades stains of biological origin, and thus increases the cleaning power. Each type of enzyme has a preferential action. Lipases act on fatty soils, amylases degrade starch, proteases degrade protein soils (blood, egg, ...) and cellulases vegetable fibers. However, enzymes are products of biological, animal or plant origin, and may be unstable under certain conditions. In particular, in a dilute aqueous medium, certain enzymes, in particular hydrolases, are unstable

These known detergent products traditionally use, as surfactants, products derived from petrochemicals. As for example, primary alcohol sulphates (PAS) and linear alkyl benzene sulphonates (LAS) are components of detergent compositions derived from petrochemistry and widely used in industry. As such, they use non-renewable raw materials, and therefore do not meet ecological concerns and sustainable development. In addition, LASs have a negative influence on enzyme stability. Renewable raw materials include products of animal origin, such as beef tallow, and products of plant origin, such as oils derived from agriculture.

State of the art

Document is known WO 01/32818 a liquid detergent composition containing a saccharide surfactant, for example an alkylpolyglucoside, and enzymes such as cellulase, amylase, and protease. Stabilization of the enzyme is achieved by a system consisting of (a) a compound containing boron and / or sodium formate and (b) a polyhydric alcohol. This stabilization system does not, however, contribute to the detergency or the germicidal power of the composition. In addition, the compositions of this document are of high viscosity and all contain less than 40% water. As such they would not be suitable for use in the form of spray. In addition, boron is a risk factor for human health, especially for fertility.

Document is known WO 01/96519 a liquid detergent composition containing (a) a detergent, (b) from 0.001 to 10% dissolved or dispersed protease, and (c) a protease stabilization system comprising from 2 to 40% of at least one saccharide selected from the group consisting of disaccharides, trisaccharides, their derivatives and mixtures thereof. This stabilization system does not, however, contribute to the detergency or the germicidal power of the composition. In the variants of this invention using a boron compound as a stabilizing agent (particularly Examples 2, 3 and 4), the same risk to human health arises. This liquid detergent composition is preferentially in concentrated form. The compositions of this document are either pourable liquids, pourable gels, or non-pourable gels. In any case, they can not be suitable for use as a spray.

The patent US6,136,778 proposes an aqueous detergent composition comprising an essential oil, a surfactant for solubilizing the essential oil, and an enzyme. However, no indication is given in this document as to the stability of the enzyme entering this composition.

Among the cleaning products available on the market, there is a first class of products comprising components derived from petrochemistry and not containing enzymes. Products of this type are generally efficient and economical. Since the main constituents of products in this class are derived from petrochemicals, these products do not contribute to reducing the use of fossil resources and, in this sense, do not meet the concerns of sustainable development. The absence of enzymes makes these products less effective in the treatment of biofouling.

Another class of cleaning products available on the market consists of formulations mainly based on renewable raw materials, but still containing no enzymes. In this class are the products "Foam bathroom" and "Soft" of the plaintiff. These products are formulated mainly from raw materials of plant or mineral origin, not derived from petrochemistry and generally having a good biodegradability. These products are mostly diluted. However, they do not include enzyme, which limits their performance in cleaning. The presence of enzymes is desirable to improve the cleaning effect of biological soils. As discussed in the patent application WO 01/85625 of the applicant, the presence of enzymes in the cleaning products also has a favorable effect on the environment by reducing the load imposed on the treatment plants. However, the use of enzymes in a detergent product requires specific know-how, in particular to solve the problem of the stability of the enzyme, especially in a diluted product.

Goals of the invention

The present invention aims to provide a liquid detergent composition, which comprises exclusively or mainly products derived from renewable raw materials, and no or few products from petrochemistry, which comprises at least one enzyme, which has good cleaning performance, in which the enzyme is stable, and which does not have the drawbacks of the prior art. In particular, the present invention aims to provide a composition in which the enzyme is stable, including in a dilute solution, and which thus allows use in the form of spray.

Summary of the invention

1. (a) de 1 à 30 % en volume d'un alkylpolyglucoside,
2. (b) de 0,01 à 3 % en volume d'une huile essentielle,
3. (c) de 0,1 à 20 % en volume d'un éther de glycol,
4. (d) de 0,01 à 10 % en volume d'une enzyme,

le complément à 100% en volume étant constitué principalement d'eau. La composition suivant l'invention permet donc de réduire la consommation de matières fossiles, et de préserver ainsi les ressources de la planète.The present invention relates to a liquid detergent composition comprising

1. (a) from 1 to 30% by volume of an alkylpolyglucoside,
2. (b) from 0.01 to 3% by volume of an essential oil,
3. (c) from 0.1 to 20% by volume of a glycol ether,
4. (d) from 0.01 to 10% by volume of an enzyme,

the complement to 100% by volume being mainly water. The composition according to the invention thus makes it possible to reduce the consumption of fossil materials, and thus to preserve the resources of the planet.

The alkylpolyglucoside is preferably selected from the group consisting of a C8-C16 glucoside, a C12-C16 glucoside, and mixtures thereof.

The essential oil is preferably selected from the group consisting of orange terpene, essential oils obtained from citrus limonum, citrus aurantium L., citrus aurantium L. ssp. bergamia, cymbopogon martinii, Thymus vulgaris, and mixtures thereof.

The glycol ether is selected from the group consisting of dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, and mixtures thereof.

The enzyme is preferably chosen from lipases, proteases, cellulases, hemicellulases, amylases, β-glucanases, xylanases, arabanases, and mixtures thereof.

The alkylpolyglucoside content is preferably between 10% and 20% by volume.

The content of the essential oil is preferably between 1% and 2% by volume.

The glycol ether content is preferably between 5% and 15% by volume.

The enzyme content is preferably between 1% and 3% by volume.

The composition has, in a preferred variant of the invention, a water content of between 85% and 97% by volume, and thus allows the use in the form of a spray.

The present invention thus also relates to the use of a composition according to the invention

This composition can be used for antifungal purpose.

Brief description of the figures

The figure 1 is a graph showing the germicidal and detergent properties of four detergent compositions.

The Figure 2a, 2b, 2c and 2d are photographs of untreated mold cultures, and treated with a bathroom cleaner according to the invention, after 24 hours and 48 hours of incubation, respectively.

The figure 3 is a set of photographs of untreated mold cultures, and treated with compositions A and B, at the initial time, after 24 hours, 48 hours and 72 hours of incubation, respectively.

The figure 4 is a set of photographs of mold cultures without any product, and with compositions C and D, at the initial time, after 24 hours, 48 hours, and 168 hours (ie one week) of incubation, respectively.

The figure 5 is a lens array of cups coated with a colored photographs butter and treated with a C8-C16 glucoside at various concentrations (1 ^st line) and a commercial detergent, ethoxylated fatty alcohol C12-C13, 8EO (2nd line) .

The figure 6 is a set of photographs of glass cups coated with a colored butter and treated respectively with (a) a formulation according to the invention, MPR5, and standard formulations representative of the classes of products previously described: (b) first class based on petrochemical and (c) second class based on renewable raw materials.

The figure 7 is a set of photographs of cups of glasses coated with a colored butter and treated with (a) a degreasing spray formulation based mainly petrochemical representative of which exists on the market and (b) a spray according to the invention, after 40 minutes soaking.

The figures 8 and 9 are graphs showing the evolution of enzymatic activity of various liquid detergent compositions, as a function of time.

Detailed description of a preferred embodiment of the invention

The applicant has discovered that, unexpectedly, the use of renewable raw materials (RPM) had a stabilizing effect on the enzymes, and that the cleaning performance was improved compared to a known formulation. Among the performance of the formulations are the detergent effect, the germicidal effect, and the anti-fungal activity.

In the context of the invention, the enzymatic activities, and their stability over time, were measured as follows: A specific substrate is placed in the presence of the enzyme. This substrate is hydrolyzed to a light absorbing product at a wavelength of 405 nm. The absorbance of a sample of this substrate is measured by means of a Thermospectronic spectrophotometer. The measured absorbance makes it possible to deduce the hydrolysis product concentration of the substrate (Beur-Lambert law), and the variation in absorbance ΔA / min is proportional to the activity of the enzyme in question.

The alkylpolyglucosides (abbreviated as APG) are compounds of general formula:

RO- (G) _x

where R is a linear or branched alkyl chain, and G is a monosaccharide such as glucose. These compounds are obtained from a fatty alcohol derived from a vegetable oil and from the monosaccharide. Among the commonly used commercially available APGs are C8 to C16 fatty alcohols glucosides (hereinafter referred to as C8-C18 glucoside) such as cocoglucoside and C12 to C16 glucoside fatty alcohols (hereinafter referred to as C12-C18 glucoside) such as laurylglucoside.

In the following table, Formulation A is a conventional formulation consisting of ethoxylated fatty alcohol, boric acid, glycol ether (Dipropylene glycol monomethyl ether), enzymes (lipase) and preservatives. Formulation B is a formulation according to the invention, in which the alkylpolyglucoside is a C8-C16 glucoside, the glycol ether is dipropylene glycol monomethyl ether, the essential oil is orange terpene and the enzyme is a lipase. The lipase activity was measured after a waiting period of 1 to 90 days. The results of these measurements show that the enzymatic activity decreases considerably less rapidly in the formulation B according to the invention than in the standard formulation A, the activity being, on average, 35% higher in the formulation B. Lipase activity ( Δ A / min) Formulation A Formulation B after 1 day 4.5 5.377 after 14 days 3,154 3,835 after 21 days 2.45 2.93 after 30 days 1,756 2,477 after 45 days 1.3 2,257 after 90 days 0.783 1,952 Medium lipase activity 2,323 3,138

Tests were carried out with formulations A and B above, in diluted form. The diluted form in water is interesting because it allows use as a spray. Lipase activity (ΔAlmin) Formulation without MPR Formulation with MPR after 90 days 0.2 > 1.5 These results show that conventional enzymatic formulations are not available in diluted form because they virtually lose all enzyme activity, and therefore must be diluted at the time of their use.

Germicidal effect and detergent

1. (1) Blanc : eau de ville
2. (2) Produit classique : Alcool gras éthoxylé + Potasse caustique + Phosphate + Conservateurs
3. (3) Produit enzymatique classique: Alcool gras éthoxylé + Acide borique + Ether de glycol (Dipropylène glycol monométhyl éther) + Enzymes (Lipase) + Conservateurs
4. (4) Produit enzymatique suivant l'invention, stabilisée par des MPR : C8-C16 glucoside + Ether de glycol (Dipropylène glycol monométhyl éther) + Terpène d'orange + Enzymes (Lipase)

dont les compositions sont données dans le tableau ci-après, dans lequel les concentrations sont exprimées en pourcentage du volume : Produit Composant Molécule conc. 1.Blanc eau eau 100% 2.Produit classique tensioactif non-ionique alcool gras éthoxylé C12-C13, 8OE 2,5% tensioactif non-ionique C8-C16 glucoside 4% séquestrant pyrophosphate tétrapotassique 7,5% alcalin potasse caustique 6% conservateurs cumène sulfonate de soude 2,5% 3.Produit enzymatique classique tensioactif non-ionique alcool gras éthoxylé 2% tensioactif non-ionique C8-C16 glucoside 2,5% acide acide borique 3% ether de glycol dipropylène glycol monométhyl éther 2,5% enzyme lipase 1,5% conservateurs cumène sulfonate de soude 4,9% 4. Produit enzymatique de l'invention tensioactif non-ionique C8-C16 glucoside 14,9% ether de glycol dipropylène glycol monométhyl éther 6% huile essentielle terpène d'orange 1,5% enzyme lipase 1,5% conservateur acide citrique 0,1% La performance d'un nettoyage peut être évaluée sur deux facteurs :

• DE (Effet détergent) : il traduit le degré d'élimination des salissures d'origine organique de la surface. Son échelle varie de 0 à 4. Plus sa valeur est élevée, plus le niveau de propreté de la surface est important.
• GE (Effet germicide) : il traduit le degré d'élimination des microorganismes adhérant à une surface. Son échelle s'étend de 0 à 8. Plus la valeur du GE est élevée, plus le nombre de microorganismes éliminés de la surface est important.

Le tableau ci-après et la figure 1 incluent les valeurs DE et GE après un nettoyage de surface à l'aide des quatre formulations décrites: GE (effet germicide) DE (effet détergent) 1.Blanc 1,26 0,22 2.Produit classique 1,8 1,58 3.Produit enzymatique classique 2,94 2,6 4.Produit enzymatique suivant l'invention 3,3 2,9 Dans la figure 1, un point représente les deux caractéristiques, effet germicide (GE) et effet détergent (DE), de chacune des quatre formulations étudiées. Le produit classique et le produit enzymatique classique se trouvent dans l'aire de nettoyage (Effet nettoyant supérieur à 1,5) Le produit enzymatique suivant l'invention se trouve à la fois dans l'aire de nettoyage et dans l'aire de désinfection (effet germicide supérieur à 3) Cette figure représente par une flèche l'amélioration de ces deux effets dans les formulations suivant l'invention. On observe donc l'amélioration des performances du produit enzymatique suivant l'invention.The germicidal and detergent effects of four formulations were compared:

1. (1) White: city water
2. (2) Classic product: Ethoxylated fatty alcohol + Caustic potash + Phosphate + Preservatives
3. (3) Conventional enzymatic product: Ethoxylated fatty alcohol + Boric acid + glycol ether (Dipropylene glycol monomethyl ether) + Enzymes (Lipase) + Preservatives
4. (4) Enzymatic product according to the invention, stabilized by MPR: C8-C16 glucoside + glycol ether (Dipropylene glycol monomethyl ether) + Orange terpene + Enzymes (Lipase)

whose compositions are given in the table below, in which the concentrations are expressed as a percentage of the volume: Product Component Molecule conc. 1.Blanc water water 100% 2.Classic product nonionic surfactant ethoxylated fatty alcohol C12-C13, 8OE 2.5% nonionic surfactant C8-C16 glucoside 4% sequestering Tetrapotassium pyrophosphate 7.5% alkaline caustic potash 6% preservatives cumene sulfonate of soda 2.5% 3.Enzymatic enzyme product nonionic surfactant ethoxylated fatty alcohol 2% nonionic surfactant C8-C16 glucoside 2.5% acid boric acid 3% glycol ether dipropylene glycol monomethyl ether 2.5% enzyme lipase 1.5% preservatives cumene sulfonate of soda 4.9% 4. Enzymatic product of the invention nonionic surfactant C8-C16 glucoside 14.9% glycol ether dipropylene glycol monomethyl ether 6% Essential oil orange terpene 1.5% enzyme lipase 1.5% Tory citric acid 0.1% The performance of a cleaning can be evaluated on two factors:

• DE (detergent effect): it reflects the degree of removal of organic soils from the surface. Its scale varies from 0 to 4. The higher its value, the higher the level of cleanliness of the surface.
• GE (Germicidal effect): it reflects the degree of elimination of microorganisms adhering to a surface. Its scale ranges from 0 to 8. The higher the EG value, the greater the number of microorganisms removed from the surface.

The table below and the figure 1 include DE and GE values after surface cleaning using the four formulations described: GE (germicidal effect) DE (detergent effect) 1.Blanc 1.26 0.22 2.Classic product 1.8 1.58 3.Enzymatic enzyme product 2.94 2.6 4.Enzymatic product according to the invention 3.3 2.9 In the figure 1 , one point represents the two characteristics, germicidal effect (GE) and detergent effect (DE), of each of the four formulations studied. The conventional product and the conventional enzymatic product are in the cleaning area (cleaning effect greater than 1.5) The enzymatic product according to the invention is found both in the cleaning area and in the disinfection area (Germicidal effect greater than 3) This figure represents by an arrow the improvement of these two effects in the formulations according to the invention. The improvement in the performance of the enzymatic product according to the invention is therefore observed.

Antifungal activity

• des agents tensioactifs issus de matières premières renouvelables,
• des huiles essentielles pures issues de plantes (indiquées dans le tableau ci-après par h.e. de ...)
• un éther de glycol, le dipropylène glycol monométhyl éther,
• des enzymes.

La composition détaillée est donnée dans le tableau ci-après: Produit Composant Molécule conc. Spray anti-fongique tensioactif non ionique C8-C16 glucoside 4% tensioactif non ionique huile de ricin hydrogénée, 40 OE 1% huile essentielle h.e. de citrus aurantium L. ssp. bergamia 0,1% huile essentielle h.e. de Citrus limonum 0,1% huile essentielle h.e. de Cymbopogon martinii 0,1% huile essentielle h.e. de Thymus vulgaris 0,1% enzyme alpha-amylase 0,2% enzyme complexe enzymatique β-glucanase, cellulase, hemicellulase, arabanase et xylanase 0,2% enzyme β-glucanase 0,2% enzyme lysophospholipase 0,2% enzyme phospholipase 0,2% éther de glycol dipropylène glycol monométhyl éther 2%
Cette composition est particulièrement adaptée à l'élimination et à la prévention de l'apparition des moisissures, par exemple dans les salles de bains. Mode opératoire:

• Le test de l'activité anti-fongique est réalisé sur base de la technique de l'antiobiogramme : un milieu de culture riche est inoculé à l'aide de microorganismes sur lesquels on désire que le produit agisse :
  • inoculum : champignons récoltés dans un endroit humide
  • 200 µl de produit est versé sur l'endroit inoculé
  • incubation durant 48 heures à 35°C

Résultats:

• La figure 2a montre le développement de la culture de moisissures après 24 heures, sur un support non traité. La figure 2b montre le même résultat, avec la composition ci-dessus. Les figures 2c et 2d montrent ce développement après 48 heures. Après 24 heures d'incubation, la moisissure commence à se développer sur la boite de pétri où aucun produit n'a été ajouté. En revanche, il n'y a aucun développement de moisissure sur dans la région où les 200 µl de la composition suivant l'invention ont été ajoutés. Après 48 heures d'incubation, la moisissure continue à se développer fortement sur le milieu inoculé où aucun produit n'a été déposé. Par contre, il n'y a toujours aucune trace de moisissure sur la boîte où la composition suivant l'invention a été rajoutée. Néanmoins, quelques microorganismes se développent autour du halo d'inhibition formé par l'ajout du produit. La composition de l'invention possède donc bien des propriétés anti-fongiques car elle empêche les champignons de se développer durant une certaine période. Ce produit est à utiliser régulièrement si on désire l'employer en traitement préventif. Une étude complémentaire a démontré l'action aussi bien des enzymes que des huiles essentielles sur la limitation de la croissance du champignon. Chaque substance active a donc son intérêt.

Antifungal activity tests were carried out according to the following procedure:
A composition according to the invention contains the following components:

• surfactants derived from renewable raw materials,
• pure essential oils from plants (indicated in the table below by he de ...)
• a glycol ether, dipropylene glycol monomethyl ether,
• enzymes.

The detailed composition is given in the table below: Product Component Molecule conc. Anti-fungal spray nonionic surfactant C8-C16 glucoside 4% nonionic surfactant hydrogenated castor oil, 40 EO 1% Essential oil he of citrus aurantium L. ssp. bergamia 0.1% Essential oil he of Citrus limonum 0.1% Essential oil he of Cymbopogon martinii 0.1% Essential oil he of Thymus vulgaris 0.1% enzyme alpha-amylase 0.2% enzyme enzymatic complex β-glucanase, cellulase, hemicellulase, arabanase and xylanase 0.2% enzyme β-glucanase 0.2% enzyme lysophospholipase 0.2% enzyme phospholipase 0.2% glycol ether dipropylene glycol monomethyl ether 2%
This composition is particularly suitable for eliminating and preventing the appearance of molds, for example in bathrooms. Operating mode:

• The test of the anti-fungal activity is carried out on the basis of the anti-biogram technique: a rich culture medium is inoculated with the aid of microorganisms on which it is desired that the product act:
  • inoculum: mushrooms harvested in a damp place
  • 200 μl of product is poured on the inoculated place
  • incubation for 48 hours at 35 ° C

Results:

• The figure 2a shows the development of mold culture after 24 hours, on an untreated support. The figure 2b shows the same result, with the composition above. The Figures 2c and 2d show this development after 48 hours. After 24 hours of incubation, the mold begins to grow on the petri dish where no product has been added. On the other hand, there is no mold growth in the region where the 200 μl of the composition according to the invention were added. After 48 hours of incubation, the mold continues to grow strongly on the inoculated medium where no product has been deposited. By cons, there is still no trace of mold on the box where the composition according to the invention was added. Nevertheless, some microorganisms develop around the inhibition halo formed by the addition of the product. The composition of the invention therefore has anti-fungal properties because it prevents fungi from developing for a certain period. This product is to be used regularly if it is desired to use it as a preventive treatment. A complementary study has demonstrated the action of both enzymes and essential oils on limiting the growth of the fungus. Each active substance is therefore of interest.

1. (A) Le produit A contient une huile essentielle et un APG (un C8-C16 glucoside), mais pas d'enzyme. Les huiles essentielles sont les huiles essentielles de thymus vulgaris, de cymbopogon martinii, de citrus limonum (0,1%).
2. (B) Le produit B, à l'inverse, contient une enzyme, mais pas d'huile essentielle, et le même APG (un C8-C16 glucoside). Les enzymes sont l'alpha-amylase, un complexe enzymatique de β-glucanase, de cellulase, d'hemicellulase, d'arabanase et de xylanase, la carbohydrase, la lysophospholipase et la phospholipase (0,2%)
3. (C) Une composition suivant l'invention, contenant un APG, une huile essentielle et une enzyme. L'APG est un C8-C16 glucoside, et l'huile essentielle est un mélange de d'huiles essentielles de thymus vulgaris, de cymbopogon martinii et de citrus limonum (0,1 %),
4. (D) Une autre composition suivant l'invention, contenant un APG, une huile essentielle et une enzyme. L'APG est un C8-C16 glucoside, et l'huile essentielle est un mélange d'huiles essentielles de citrus limonum et de citrus aurantium L. ssp. bergamia (0,1%) (huiles essentielles obtenues à partir d'agrumes).

Un volume de 200 µl de chaque produit est versé sur une moisissure repiquée sur boîtes de pétri en milieu riche. L'inoculum sur boîtes de pétri est préparé à partir d'un bout de gélose déjà contaminé par une moisissure. Les boîtes de pétri sont mises en incubation à 35°C durant 72 heures et comparées à un blanc. Les résultats suivants sont observés :The Applicant has discovered that the compositions according to the invention, comprising an APG, an essential oil, a glycol ether, and an enzyme have unexpected interesting characteristics. To demonstrate this synergistic effect, the development of molds in untreated petri dishes (hereinafter referred to as "white") and test compositions was compared. The following tests were carried out with the following compositions:

1. (A) Product A contains an essential oil and APG (a C8-C16 glucoside), but no enzyme. The essential oils are the essential oils of thymus vulgaris, cymbopogon martinii, citrus limonum (0.1%).
2. (B) Product B, conversely, contains an enzyme, but no essential oil, and the same APG (a C8-C16 glucoside). Enzymes are alpha-amylase, an enzyme complex of β-glucanase, cellulase, hemicellulase, arabanase and xylanase, carbohydrase, lysophospholipase and phospholipase (0.2%)
3. (C) A composition according to the invention, containing an APG, an essential oil and an enzyme. APG is a C8-C16 glucoside, and the oil essential is a blend of essential oils of thymus vulgaris, cymbopogon martinii and citrus limonum (0.1%),
4. (D) Another composition according to the invention, containing an APG, an essential oil and an enzyme. APG is a C8-C16 glucoside, and the essential oil is a blend of essential oils of citrus limonum and citrus aurantium L. ssp. bergamia (0.1%) (essential oils obtained from citrus fruits).

A volume of 200 .mu.l of each product is poured onto a mold transplanted on petri dishes in a rich medium. The inoculum on petri dishes is prepared from a piece of agar already contaminated with mold. The petri dishes are incubated at 35 ° C for 72 hours and compared to a blank. The following results are observed:

A first series of tests aims to evaluate the antifungal effect of each of the components of the compositions according to the invention. Products A, B, C and D, described above, are compared. The figure 3a shows the state of development of the mold at the initial time. The figure 3b shows the state of development of the mold after 24 hours. It is observed that the mycelium of the mold begins to extend circularly from where the contaminant was deposited. In the box where compositions A and B have been applied, no mold growth is observed.
The figure 3c shows the state of development of the mold after 48 hours. After 48 hours of incubation, white mold tripled its coverage area from the initial inoculation location. Some points of mold development are to be noted for the product A, containing an essential oil and the product B, containing an enzyme, but this development is limited.
The figure 3c shows the state of development of the mold after 72 hours. After 72 hours of incubation, the mycelium constituting the mold of white has further spread. The mold spots for product A and B have grown but the amount of mycelium to white is limited. In addition, mold does not develop from the point of inoculation (at center) but rather from the periphery, indicating the presence of an inhibition zone triggered by the antifungal activity of the two products A and B.

A second series of tests aims to evaluate the antifungal effect of each two types of essential oils used in compositions according to the invention and compares compositions C and D and "white". The figure 4a shows the state of development of the mold at the initial time.
The figure 4b shows the state of development of the mold after 24 hours. After 24 hours of incubation, the mold begins to develop for the white. There is no development for petri dishes containing compositions C and D.
The figure 4c shows the state of development of the mold after 48 hours of incubation. The mycelium contained in the white has grown considerably. We begin to see a slight development of mold for compositions C and D but this development is much less pronounced than for white. This less important development demonstrates the antifungal activity of compositions C and D.
The figure 4d shows the state of development of the mold after one week of incubation.
After a week, the mycelium of mold completely filled the entire surface of the control. The surface of the media where compositions C and D have been deposited is still not completely covered. In addition, the development of mold is less pronounced on the composition C side than the composition D. This is quite normal because the essential oils based on herbs (clove, palmarosa, etc ...) are recognized for their bactericidal and anti-fungal power. The citrus-based essential oils (lemon, bergamot, etc.) have a less pronounced bactericidal and anti-fungal effect.

It is concluded from these tests, on the one hand, that enzymes and essential oils (derived from aromatics) each have antifungal activity. These two types of renewable raw materials can therefore work in synergy because they have different modes of action on microorganisms. These results highlight an antifungal effect of enzymes used in the formulations of the invention. Then, the choice of the essential oil mixture determines the effectiveness of the anti-fungal activity in the more or less long term.

Detergent effect

• les solvants présentant le pouvoir dégraissant le plus important, parmi la gamme des solvants essayés sont les huiles essentielles terpènes d'orange et de citron, les propylène glycol éthers (le propylène glycol monométhyl éther et le dipropylène glycol monométhyl éther).
  Ces deux séries d'essais conduisent également aux conclusions suivantes :
  • les solvants (huiles essentielles et éthers de glycol) agissent rapidement sur la graisse et puis n'agissent plus ;
  • les tensioactifs (un C8-C16 glucoside) agissent plus lentement mais pendant longtemps, jusqu'à élimination des dépôts de graisse.
    Les compositions suivant l'invention allient donc l'effet dégraissant à court terme des solvants avec l'effet dégraissant à plus long terme des C8-C16 glucosides.

It has been sought to evaluate the effectiveness of the constituents used in the compositions according to the invention, taken alone, by comparing them with a usual product. The experiment involves coating a glass cup with a fixed amount of red colored butter. The product to be tested is brought into contact with the cup, without agitation, in order to check the degreasing efficiency of the formula.
In a first series of tests, the results of which are shown in figure 5 the degreasing effect of a C8-C16 glucoside, which is a surfactant used in the compositions of the invention, was compared with that of a C12-C13, 8OE ethoxylated fatty alcohol, a product derived from petrochemistry, which is a surfactant commonly used in detergent compositions at different concentrations. These two test surfactants have been selected as effective surfactants, derived on the one hand from a plant origin, and on the other hand petrochemicals. The results of the experiment, represented in figure 5 show that these two surfactants are effective, with a significantly better effect for the plant-based surfactant, particularly at higher concentrations, of 0.6 to 1%.
In a second series of tests, not shown, the efficiency of several solvents was compared. The results of this second series of tests are as follows:

• the solvents with the most important degreasing power, among the range of solvents tested are the essential oils terpenes of orange and lemon, propylene glycol ethers (propylene glycol monomethyl ether and dipropylene glycol monomethyl ether).
  These two series of tests also lead to the following conclusions:
  • the solvents (essential oils and glycol ethers) act quickly on the fat and then no longer act;
  • surfactants (a C8-C16 glucoside) act more slowly but for a long time until fat deposits are removed.
    The compositions according to the invention thus combine the short-term degreasing effect of solvents with the longer-term degreasing effect of C8-C16 glucosides.

It has also been sought to demonstrate the effectiveness of the compositions according to the invention, comprising an alkylpolyglucoside, an essential oil, a glycol ether and an enzyme with respect to the two classes of products known from the prior art. The experiment consists in coating a glass dish with a fixed and known quantity of colored butter in red. The test composition is brought into contact with the cup, without stirring, in order to verify the effectiveness of the formula. 50 ml of a 10% solution of the test composition are poured into the cup, the mixture is left to act for 40 minutes at room temperature, then the mixture is heated at 105 ° C. for 20 minutes to remove all traces of water, and weighs to determine the amount of colored butter removed. The compositions according to the invention, MPRF1 to MPRF6, are compared with products of the first class, the product "Reatout" of the applicant, and a formulation representative of this class of products, and products of the second class, the "Soft" product of the applicant, and a representative formulation of this other class of products.
The compositions of Reatout and Soft products are as follows: Component Molecule Conc. Reatout Nonionic surfactant ethoxylated fatty alcohol C12-C13, 8OE 16% Alcohol isopropanol 4% dispersed polyacrylic acid 2% ketone pyrolidone 4% Glycol ether dipropylene glycol monomethyl ether 16% Soft Anionic surfactant lauryl ether sodium sulphate, 2-3 EO 40% Nonionic surfactant coconut fatty acid diethanolamide 4.90% Glycol ether dipropylene glycol monomethyl ether 16% The compositions of the representative products of the first and second classes are as follows: Component Molecule conc. Class 1 indicator anionic surfactant lauryl ether sodium sulphate, 2-3 EO 3% nonionic surfactant ethoxylated fatty alcohol C12-C13, 8OE 8% dispersed polyacrylate 1% glycol ether propylene glycol monomethylether 2% alcohol isopropanol 2% sequestering sodium citrate 3% Class 2 witness anionic surfactant liquid soap based on vegetable oil (C18) 4% anionic surfactant lauryl ether sodium sulphate, 2-3 EO 2% nonionic surfactant C8-C16 glucoside 6% alcohol ethanol 4% sequestering sodium citrate 3% vegetable oil pine oil 0.2% The effectiveness of each of the formulations, determined as being the percentage by weight of colored butter removed, is given in the table below: Formulation APG % HEY % Glycol ether % Enzyme % efficiency MPRF 1 C8-C16 glucoside 10 orange terpene 1 propylene glycol monomethyl ether 8 lipase 1 78% MPRF 2 C12-C16 glucoside 2 orange terpene 1 propylene glycol monomethyl ether 8 lipase 1 73% C8-C16 glucoside 10 MPRF 3 C8-C16 glucoside 10 he of citrus limonum 1 dipropylene glycol monomethyl ether 8 lipase 1 50% MPRF 4 C8-C16 glucoside 10 he of citrus limonum 1 propylene glycol monomethyl ether 8 lipase 1 62% MPRF 5 C12-C16 glucoside 2 he of citrus limonum 1 propylene glycol monomethyl ether 8 lipase 1 51% C8-C16 glucoside 10 MPRF 6 C8-C16 glucoside 10 Bergamot HE 1 dipropylene glycol monomethyl ether 8 lipase 1 62% Class 1: Reatout 0 0 24% Witness 0 0 17% Class 2: Soft 0 0 25% Witness 0 0 30% The figure 6 represents the evolution after 1 hour of soaking. It can be seen that the composition according to the invention MPR5 ( figure 6 a ) is more effective in degreasing than Class 1 products ( figure 6 b ) and 2 ( figure 6 c ). This improvement in the degreasing power of a composition according to the invention can be explained by the synergy of the action of the enzymes (lipase) and the other components of the product (C8-C16 glucoside, glycol ether, essential oils).

Use as a spray

It has also been sought to demonstrate the effectiveness of a composition according to the invention which can be used in spray form, that is to say a composition which is strongly diluted with water, comprising an alkylpolyglucoside, an essential oil and an ether. glycol and an enzyme. The effectiveness of this composition is compared with that of a spray cleaning formulation multi-purpose representative of what exists on the market. The compositions of these two formulations and their effectiveness, determined as being the percentage by weight of colored butter removed, are detailed in the table below: Product Component Molecule conc. Efficiency Pr. Enz. MPR spray nonionic surfactant C8-C16 glucoside 3% 60.6% Essential oil orange terpenes 0.2% Glycol ether dipropylene glycol monomethyl ether 1% enzymes lipase 0.1% conservatives Citric acid 0.03% water 95.67% Sample Multi-Use Spray anionic surfactant lauryl ether sodium sulphate, 2-3 EO 0.5% 44% nonionic surfactant C8-C16 glucoside 0.5% nonionic surfactant ethoxylated fatty alcohol C12-C13, 8OE 0.5% amphoteric surfactant amidopropylbutane (C12 / 18) 0.5% alkaline agent soda ash 0.5% alkaline agent caustic soda 0.025% glycol ether dipropylene glycol monomethyl ether 1% sequestering sodium citrate 0.5% sequestering phosphonate 0.025% water 95.95% The test is also carried out in glass cups coated with a thin layer of colored butter using a red dye. A quantity of 0.5 g of butter per cup is spread evenly over the entire surface. The Test compositions are contacted with the cups, without agitation, in order to verify the effectiveness of the formula. 50 ml of a pure solution of each test composition are poured into the cup. This efficiency test is performed without mechanical action and at room temperature. The results are observed after 40 minutes (see figure 7 ). From the first minutes, the spray according to the invention ( figure 7b ) attack the fat while the product of the market ( figure 7a ) almost does not work. After 40 minutes, a greater amount of the fat was peeled off by the spray according to the invention while a significant amount of fat is still present on the cup treated with the product market. In addition, the spray of the invention emulsifies the fat much better than the product of the market. The pH variation, before and after action of the product, for the composition according to the invention is 0.27, whereas it is zero for the product of the market. The emulsion obtained with the spray according to the invention was therefore acidified. This indicates that the lipases contained in the formulation acted well on the triglycerides by converting a portion of the fat into fatty acids, resulting in the acidification of the mixture. Finally, the new spray according to the invention, based on MPR, has improved properties compared to products on the market. Thanks to its powerful synergistic natural elements (C8-C16 glucoside, orange terpene, lipase), it manages to tackle fat efficiently and quickly

Stability of enzymes

Finally, it was sought to highlight the stability characteristics of the enzymes in various formulations. The figure 8 represents the evolution of the enzymatic activities of the compositions according to the invention MPRF1 to MPRF6, and a conventional enzymatic composition, without MPR, the product "Degres L" of the applicant. It is found that in all cases, the enzymatic activity of the compositions according to the invention is greater than that of the composition "Degrees L". The stability of the enzyme has also been tested in various formulations listed in the table below. MPR1 contains no essential oil or glycol ether. In MPR2, a glycol ether was added: dipropylene glycol monomethyl ether. In MPR3, a terpene is present, but no glycol ether. In MPR4, there is no MPR. MPR5 is a composition according to the invention. MPR6 is comparable to MPR1, but the surfactant is a commercial product from the petrochemical industry. MPR7 contains a glycol ether and an enzyme. Formulation surfactant % HEY % Glycol ether % Enzyme % MPR 1 C8-C16 glucoside 10 lipase 1 MPR 2 C8-C16 glucoside 10 dipropylene glycol monomethyl ether 8 lipase 1 MPR 3 C8-C16 glucoside 10 orange terpene 1 lipase 1 MPR 4 orange terpene 1 dipropylene glycol monomethyl ether 10 lipase 1 MPR 5 C8-C16 glucoside 10 orange terpene 1 dipropylene glycol monomethyl ether 8 lipase 1 MPR 6 ethoxylated fatty alcohol C12-C13,80E 10 lipase 1 MPR 7 dipropylene glycol monomethyl ether 8 lipase 1 The figure 9 represents the evolution of the enzymatic activities of these compositions. It is found that the orange terpene (MPR4 composition) and a C8-C16 glucoside (MPR1 composition) are two MPR that stabilize the enzyme very strongly. It is also found that the dipropylene glycol monomethyl ether (composition MPR7) gives a better stability than the ethoxylated fatty alcohol C12-C13.8OE (composition MPR6). The glycol ether is present in the formulation because its degreasing role is essential. Finally, it is important to note that the enzymatic activity obtained with a composition containing a 100% vegetable surfactant (C8-C16 glucoside: MPR1) is better than that obtained with a 100% petrochemical surfactant (ethoxylated fatty alcohol C12-C13, 8OE : MPR7).

Claims (12)

1. Liquid detergent composition which can be used in the form of a spray, comprising:

   (a) from 1 to 30 volume % of an alkylpolyglucoside,

   (b) from 0.01 to 3 volume % of a pure essential oil derived from plants,

   (c) from 0.1 to 20 volume % of glycol ether,

   (d) from 0.01 to 10 volume % of an enzyme,
   the complement to 100 volume % being mainly constituted of water.
2. Composition according to claim 1, characterized in that the alkylpolyglucoside is selected from the group consisting in C8-C16 glucoside, C12-C16 glucoside, and mixtures thereof.
3. Composition according to any one of the preceding claims, characterized in that the essential oil is selected from the group consisting in orange terpene, essential oils obtained from citrus limonum, citrus aurantium L., citrus aurantium L. ssp. bergamia, cymbopogon martinii, Thymus vulgaris, and mixtures thereof.
4. Composition according to any one of the preceding claims, characterized in that the glycol ether is selected from the group consisting in dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, and mixtures thereof.
5. Composition according to any one of the preceding claims, characterized in that the enzyme is selected from:

   - lipases,

   - proteases,

   - cellulases,

   - hemicellulases,

   - amylases,

   - β-glucanases,

   - xylanases,

   - arabanases,
   and mixtures thereof.
6. Composition according to any one of the preceding claims, characterized in that the alkylpolyglucoside content is between 10 volume % and 20 volume %.
7. Composition according to any one of the preceding claims, characterized in that the essential oil content is between 1 volume % and 2 volume %.
8. Composition according to any one of the preceding claims, characterized in that the glycol ether content is between 5 volume % and 15 volume %.
9. Composition according to any one of the preceding claims, characterized in that the enzyme content is between 1 volume % and 3 volume %.
10. Composition according to any one of the preceding claims, for being used in the form of a spray, characterized in that the water content is between 85 volume % and 97 volume %.
11. Use of the composition according to any one of the preceding claims in the form of a spray.
12. Use according to claim 11 for antifungal purposes.

Images