WO2007095999A1 - Liquid detergent composition containing an enzyme - Google Patents

Liquid detergent composition containing an enzyme Download PDF

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Publication number
WO2007095999A1
WO2007095999A1 PCT/EP2006/060244 EP2006060244W WO2007095999A1 WO 2007095999 A1 WO2007095999 A1 WO 2007095999A1 EP 2006060244 W EP2006060244 W EP 2006060244W WO 2007095999 A1 WO2007095999 A1 WO 2007095999A1
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WO
WIPO (PCT)
Prior art keywords
volume
enzyme
composition according
composition
product
Prior art date
Application number
PCT/EP2006/060244
Other languages
French (fr)
Inventor
Gauthier Boels
Sébastien FASTREZ
Gordon Blackman
Original Assignee
Realco S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Realco S.A. filed Critical Realco S.A.
Priority to ES06708495T priority Critical patent/ES2329931T3/en
Priority to DE602006007880T priority patent/DE602006007880D1/en
Priority to PCT/EP2006/060244 priority patent/WO2007095999A1/en
Priority to EP06708495A priority patent/EP1987125B1/en
Publication of WO2007095999A1 publication Critical patent/WO2007095999A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0043For use with aerosol devices
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes

Definitions

  • 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.
  • 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 surface-active agents, products derived from petrochemistry.
  • 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.
  • 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.
  • WO 01/32818 discloses 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.
  • 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.
  • boron is a risk factor for human health, especially for fertility.
  • WO 01/96519 discloses a liquid detergent composition containing (a) a detergent, (b) from 0.001 to 10% dissolved or dispersed protease, and (c) a protease stabilization system having 2 at 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.
  • 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.
  • 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.
  • US Patent 6,136,778 proposes an aqueous detergent composition comprising an essential oil, a surfactant for solubilizing the essential oil, and an enzyme.
  • an enzyme for solubilizing the essential oil
  • no indication is given in this document as to the stability of the enzyme entering this composition.
  • there is a first class of products comprising constituents from petrochemistry and not involving enzymes. Products of this type are generally efficient and economical.
  • 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.
  • 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.
  • 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 derived 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 disadvantages of the prior art.
  • 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.
  • the present invention relates to a liquid detergent composition
  • a liquid detergent composition comprising
  • 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, ⁇ -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
  • the composition has, in a preferred embodiment of the invention, a water content of between 85% and 97% by volume, and thus allows the use as 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.
  • Figure 1 is a graph showing the germicidal and detergent properties of four detergent compositions.
  • Figures 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.
  • 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.
  • FIG. 4 is a set of photographs of mold cultures without any product, and with compositions C and D, at the initial moment, after 24 hours, 48 hours, and 168 hours (ie one week) of incubation, respectively.
  • 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, the C12-C13 ethoxylated fatty alcohol , 8OE (2nd line).
  • FIG. 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 typical formulations representative of the classes of products previously described: (b) first class petrochemical and (c) second class based on renewable raw materials.
  • FIG. 7 is a set of photographs of glass cups coated with a colored butter and treated with (a) a degreasing spray formulation based primarily on petrochemicals representative of which exists on the market and (b) a spray according to the invention. invention, after 40 minutes of soaking.
  • Figures 8 and 9 are graphs showing the evolution of enzymatic activity of various liquid detergent compositions, as a function of time.
  • the measured absorbance makes it possible to deduce the concentration of hydrolysis product of the substrate (Beer-Lambert law), and the variation of absorbance ⁇ A / 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.
  • R is a linear or branched alkyl chain
  • G is a monosaccharide such as glucose.
  • 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.
  • 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.
  • Tests were carried out with the formulations A and B above, in diluted form.
  • the diluted form in water is interesting because it allows use as a spray.
  • Enzymatic product according to the invention stabilized by MPR: C8-C16 glucoside + glycol ether (Dipropylene glycol monomethyl ether)
  • one dot 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 [0036] Antifungal activity tests were carried out according to the following procedure:
  • a composition according to the invention contains the following components:
  • glycol ether dipropylene glycol monomethyl ether
  • This composition is particularly suitable for eliminating and preventing the appearance of molds, for example in bathrooms. Operating mode:
  • 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:
  • Figure 2a shows the development of the mold culture after 24 hours on an untreated support.
  • Figure 2b shows the same result, with the composition above.
  • Figures 2c and 2d show this development after 48 hours.
  • the mold begins to grow on the petri dish where no product has been added.
  • the mold continues to grow strongly on the inoculated medium where no product has been deposited.
  • the composition according to the invention was added. Nevertheless, some microorganisms develop around the inhibition halo formed by the addition of the product.
  • 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.
  • compositions according to the invention comprising an APG, an essential oil, a glycol ether, and an enzyme have unexpected interesting characteristics.
  • APG an essential oil
  • glycol ether an enzyme
  • test compositions were compared. The following tests were carried out with the following compositions:
  • 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%).
  • 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 ⁇ -glucanase, cellulase, hemicellulase, arabanase and xylanase, carbohydrase, lysophospholipase and phospholipase (0.2%)
  • a composition according to the invention containing an APG, an essential oil and an enzyme.
  • APG is a C8-C16 glucoside
  • the oil essential is a blend of essential oils of thymus vulgaris, cymbopogon martinii and citrus limonum (0.1%),
  • composition according to the invention containing an APG, an essential oil and an enzyme.
  • APG is a C8-C16 glucoside
  • 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.
  • Petri dishes are incubated at 35 0 C for 72 hours and compared to a blank.
  • the following results are observed: [0038]
  • a first series of tests aims at evaluating 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.
  • Figure 3a shows the state of development of the mold at the initial time.
  • 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.
  • 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.
  • 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, which indicates the presence of an inhibition zone triggered by the antifungal activity of the two products A and B.
  • a second series of tests aims at evaluating the effect antifungal of each two types essential oils used in compositions according to the invention and compares the compositions C and D and the "white”.
  • Figure 4a shows the state of development of the mold at the initial time.
  • 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.
  • 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 significant development is indicative of the antifungal activity of compositions C and D.
  • Figure 4d shows the state of development of 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.
  • the development of mold is less pronounced in the composition C than in the composition D. This is quite normal because the essential oils based on herbs (clove, palmarosa.etc.) Are recognized for their power.
  • the citrus-based essential oils have a lower bactericidal and anti-fungal potency. It is concluded from these tests, on the one hand, that the 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.
  • compositions of the invention taken in isolation, by comparing them to 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.
  • the solvents having 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).
  • compositions according to the invention thus combine the short-term degreasing effect of solvents with the longer-term degreasing effect of C8-C16 glucosides.
  • compositions according to the invention comprising an alkylpolyglucoside, an essential oil, a glycol ether and an enzyme with respect to the two classes of known products of 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 dish, 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.
  • compositions according to the invention 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:
  • compositions of the representative products of the first and second classes are as follows:
  • Figure 6 shows the evolution after 1 hour of soaking. It can be seen that the composition according to the invention MPR5 (FIG. 6 a) is more effective in degreasing power than products of the class 1 market (FIG. 6b) and 2 (FIG. 6c). 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).
  • the enzymes lipase
  • compositions according to the invention that can be used in spray form, that is to say a composition which is strongly diluted with water, comprising an alkylpolyglucoside, an essential oil. , a glycol ether 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:
  • 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 (FIG. 7b) attacks the fat while the product of the market (FIG. 7a) hardly acts.
  • the spray according to 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.
  • 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
  • FIG. 8 represents the evolution of the enzymatic activities of the compositions according to the invention MPRF1 to MPRF6, and of a conventional enzymatic composition, without MPR, the product "Degrees 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.
  • Figure 9 shows the evolution of 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.

Abstract

The present invention relates to a liquid detergent composition obtained from renewable starting materials, comprising from 1% to 30% by volume of an alkylpolyglucoside, from 0.01% to 3% by volume of an essential oil, from 0.1% to 10% by volume of a glycol ether and from 0.01% to 10% by volume of an enzyme, the remainder being mainly water. It relates in particular to such a composition, highly diluted, for use in the form of a spray, in which the enzyme is stable.

Description

Composition détergente liquide contenant une enzyme Liquid detergent composition containing an enzyme
Objet de l'inventionObject of the invention
[0001] La présente invention a pour objet une composition détergente liquide obtenue à partir de matières premières renouvelables et comportant une enzyme. La composition détergente concerne une utilisation dans des applications domestiques et industrielles.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.
Arrière-plan technologique [0002] Des produits détergents et de nettoyage contenant des enzymes sont connus et utilisés dans les applications domestiques, principalement dans les applications de lessive et de lave-vaisselle, et dans l'industrie, par exemples les industries alimentaires, pour les sols, les murs et le nettoyage en place. Dans les produits pour usage domestique, l'usage des enzymes est cependant moins répandu. En effet, l'adjonction d'enzymes augmente le coût de ces produits. Il nécessite également un savoir-faire, en particulier pour prévenir tout risque d'allergie. Il est connu que l'adjonction d'enzymes à une composition détergente liquide permet de dégrader rapidement des salissures d'origine biologiques, et augmente ainsi le pouvoir nettoyant. Chaque type d'enzyme a une action préférentielle. Les lipases agissent sur les salissures grasses, les amylases dégradent l'amidon, les protéases dégradent les salissures protéiniques (sang, œuf, ...) et les cellulases les fibres végétales. Cependant, les enzymes sont des produits d'origine biologique, animale ou végétale, et peuvent s'avérer instables dans certaines conditions. En particulier, dans un milieu aqueux dilué, certaines enzymes, en particulier les hydrolases, sont instables [0003] Ces produits détergents connus utilisent traditionnellement comme agents tensioactifs des produits issus de la pétrochimie. A titre d'exemple, les sulfates d'alcools primaires (PAS) et les alkyl benzène sulfonates linéaires (LAS) sont des constituants de compositions détergentes issus de la pétrochimie, et largement utilisés dans l'industrie. A ce titre, elles font appel à des matières premières non renouvelables, et ne rencontrent donc pas les préoccupations écologiques et de développement durable. De plus, les LAS ont une influence négative sur la stabilité des enzymes. Les matières premières renouvelables comprennent des produits d'origine animale, tels que le suif de bœuf, et des produits d'origine végétale, telles que les huiles issues de l'agriculture.BACKGROUND [0002] Cleaning and detergent 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 cleaning up. 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. [0003] These known detergent products traditionally use, as surface-active agents, products derived from petrochemistry. 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.
État de la techniqueState of the art
[0004] On connaît du document WO 01/32818 une composition liquide détergente contenant un agent tensioactif à base de saccharides, par exemple un alkylpolyglucoside, et des enzymes telles que la cellulase, l'amylase, et la protéase. La stabilisation de l'enzyme est obtenue par un système constitué de (a) un composé contenant du bore et/ou du formate de sodium et (b) un alcool polyhydrique. Ce système de stabilisation ne contribue cependant en rien au pouvoir détergent ou au pouvoir germicide de la composition. De plus, les compositions de ce document sont de viscosité élevée et contiennent toutes moins de 40% d'eau. A ce titre elles ne conviendraient donc pas à une utilisation sous forme de spray. De plus, le bore est un élément présentant des risques pour la santé humaine, en particulier pour la fécondité. [0005] On connaît du document WO 01/96519 une composition liquide détergente contenant (a) un détergent, (b) de 0.001 à 10% de protéase dissoute ou dispersée, et (c) un système de stabilisation de la protéase comportant de 2 à 40% d'au moins un saccharide choisi parmi le groupe constitué des disaccharides, des trisaccharides, de leurs dérivés et de leurs mélanges. Ce système de stabilisation ne contribue cependant en rien au pouvoir détergent ou au pouvoir germicide de la composition. Dans les variantes de cette invention utilisant un composé du bore comme agent stabilisant (en particulier les exemples 2, 3 et 4), le même risque pour la santé humaine se présente. Cette composition liquide détergente est préférentiellement sous forme concentrée. Les compositions de ce document sont soit des liquides versables, soit des gels versables, soit des gels non versables. En aucun cas, ils ne peuvent convenir pour une utilisation sous forme de spray. [0006] Le brevet US 6,136,778 propose une composition détergente aqueuse comprenant une huile essentielle, un agent tensioactif pour solubiliser l'huile essentielle, et une enzyme. Cependant, aucune indication n'est donnée dans ce document quant à la stabilité de l'enzyme entrant dans cette composition. [0007] Parmi les produits nettoyants disponibles sur le marché, on connaît une première classe de produits comportant des constituants issus de la pétrochimie et ne comportant pas d'enzymes. Les produits de ce type sont en général efficaces et économiques. Les constituants principaux des produits de cette classe étant issus de la pétrochimie, ces produits ne participent pas à réduire l'utilisation des ressources fossiles et, en ce sens, ne répondent pas aux préoccupations de développement durable. L'absence d'enzymes rend ces produits moins performants dans le traitement de salissures d'origine biologique. [0008] Une autre classe de produits nettoyants disponibles sur le marché est constituée de formulations principalement à base de matières premières renouvelables, mais ne comportant toujours pas d'enzymes. Dans cette classe figurent les produits « Mousse salle de bains » et « Soft » de la demanderesse. Ces produits sont formulés principalement à partir de matières premières d'origine végétale ou minérale, non issue de la pétrochimie et présentant généralement une bonne biodégradabilité. Ces produits sont la plupart du temps fort dilués. Ils ne comportent cependant pas non plus d'enzyme, ce qui limite leurs performances au nettoyage. La présence d'enzymes est désirable pour améliorer l'effet nettoyant de salissures biologiques. Ainsi que discuté dans la demande de brevet WO 01/85625 de la demanderesse, la présence d'enzymes dans les produits nettoyants a également un effet favorable sur l'environnement en diminuant la charge imposée aux stations d'épuration. La mise en œuvre d'enzymes dans un produit détergent requiert cependant un savoir-faire spécifique, en particulier pour résoudre le problème de la stabilité de l'enzyme, en particulier dans un produit dilué.[0004] WO 01/32818 discloses 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. WO 01/96519 discloses a liquid detergent composition containing (a) a detergent, (b) from 0.001 to 10% dissolved or dispersed protease, and (c) a protease stabilization system having 2 at 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. US Patent 6,136,778 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 constituents from petrochemistry and not involving 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 not containing 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.
Buts de l'invention [0009] La présente invention vise à fournir une composition détergente liquide, qui comporte exclusivement ou principalement des produits issus de matières premières renouvelables, et pas ou peu de produits issus de la pétrochimie, qui comporte au moins une enzyme, qui présente de bonnes performances au nettoyage, dans laquelle l'enzyme est stable, et qui ne présente pas les inconvénients de l'art antérieur. En particulier, la présente invention vise à fournir une composition dans laquelle l'enzyme est stable, y compris dans une solution diluée, et qui permet ainsi une utilisation sous forme de spray.OBJECTS OF THE INVENTION [0009] 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 derived 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 disadvantages 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.
Résumé de l'inventionSummary of the invention
[0010] La présente invention se rapporte à une composition détergente liquide comprenantThe present invention relates to a liquid detergent composition comprising
(a) de 1 à 30 % en volume d'un alkylpolyglucoside,(a) from 1 to 30% by volume of an alkylpolyglucoside,
(b) de 0,01 à 3 % en volume d'une huile essentielle, (c) de 0,1 à 20 % en volume d'un éther de glycol,(b) from 0.01 to 3% by volume of an essential oil, (c) from 0.1 to 20% by volume of a glycol ether,
(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. [0011] L'alkylpolyglucoside est choisi de préférence parmi le groupe consistant en un C8-C16 glucoside, un C12-C16 glucoside , et leurs mélanges. [0012] L'huile essentielle est choisie de préférence parmi le groupe consistant en le terpène d'orange, les huiles essentielles obtenues à partir du citrus limonum, du citrus aurantium L., du citrus aurantium L. ssp. bergamia, du cymbopogon martinii, du Thymus vulgaris, et leurs mélanges.(d) from 0.01 to 10% by volume of an enzyme, the 100% by volume supplement consisting mainly of 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.
[0013] L'éther de glycol est choisi parmi le groupe consistant en le dipropylène glycol monométhyl éther, le propylène glycol monométhyl éther, et leurs mélanges. [0014] L'enzyme est choisie de préférence parmi les lipases, les protéases, les cellulases, les hémicellulases, les amylases, les β-glucanases, les xylanases, les arabanases, et leurs mélanges.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.
[0015] La teneur en alkylpolyglucoside est préférentiellement comprise entre 10% et 20% en volume.The alkylpolyglucoside content is preferably between 10% and 20% by volume.
[0016] La teneur en l'huile essentielle est préférentiellement comprise entre 1% et 2% en volume.The content of the essential oil is preferably between 1% and 2% by volume.
[0017] La teneur en éther de glycol est préférentiellement comprise entre 5% et 15% en volume. [0018] La teneur en enzyme est préférentiellement comprise entreThe glycol ether content is preferably between 5% and 15% by volume. The enzyme content is preferably between
1% et 3% en volume.1% and 3% by volume.
[0019] La composition a, dans une variante préférée de l'invention, une teneur en eau est comprise entre 85% et 97% en volume, et permet ainsi l'utilisation sous forme de spray. [0020] La présente invention se rapporte donc également à l'utilisation d'une composition suivant l'inventionThe composition has, in a preferred embodiment of the invention, a water content of between 85% and 97% by volume, and thus allows the use as a spray. The present invention thus also relates to the use of a composition according to the invention
[0021] Cette composition peut être utilisée dans un but antifongique.This composition can be used for antifungal purpose.
Brève description des figures [0022] La figure 1 est un graphique représentant les propriétés germicides et l'effet détergent de quatre compositions détergentes. [0023] Les figure 2a, 2b, 2c et 2d sont des photographies de cultures de moisissures non traitées, et traitées avec un produit nettoyant pour salle de bains suivant l'invention, après 24heures et 48 heures d'incubation, respectivement.Brief Description of the Figures [0022] Figure 1 is a graph showing the germicidal and detergent properties of four detergent compositions. Figures 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.
[0024] La figure 3 est un ensemble de photographies de cultures de moisissures non traitées, et traitées avec les compositions A et B, à l'instant initial, après 24 heures, 48 heures et 72 heures d'incubation, respectivement. [0025] La figure 4 est un ensemble de photographies de cultures de moisissures sans aucun produit, et ave les compositions C et D, à l'instant initial, après 24 heures, 48 heures, et 168 heures (soit une semaine) d'incubation, respectivement. [0026] La figure 5 est un ensemble de photographies de coupelles de verres enduites d'un beurre coloré et traité avec un C8-C16 glucoside à diverses concentrations (1ere ligne) et un détergent commercial, l'alcool gras éthoxylé C12-C13, 8OE (2eme ligne). [0027] La figure 6 est un ensemble de photographies de coupelles de verres enduites d'un beurre coloré et traitées avec respectivement (a) une formulation suivant l'invention, MPR5, et des formulations types représentatives des classes de produits précédemment décrites : (b) première classe à base pétrochimique et (c) deuxième classe à base de matières premières renouvelables.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. [0025] FIG. 4 is a set of photographs of mold cultures without any product, and with compositions C and D, at the initial moment, after 24 hours, 48 hours, and 168 hours (ie one week) of incubation, respectively. [0026] 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, the C12-C13 ethoxylated fatty alcohol , 8OE (2nd line). FIG. 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 typical formulations representative of the classes of products previously described: (b) first class petrochemical and (c) second class based on renewable raw materials.
[0028] La figure 7 est un ensemble de photographies de coupelles de verres enduites d'un beurre coloré et traitées avec (a) une formulation spray dégraissant à base principalement pétrochimique représentative de qui existe sur le marché et (b) un spray suivant l'invention, après 40 minutes de trempage. [0029] Les figures 8 et 9 sont des graphiques représentant l'évolution de l'activité enzymatique de diverses compositions détergentes liquides, en fonction du temps.[0028] FIG. 7 is a set of photographs of glass cups coated with a colored butter and treated with (a) a degreasing spray formulation based primarily on petrochemicals representative of which exists on the market and (b) a spray according to the invention. invention, after 40 minutes of soaking. Figures 8 and 9 are graphs showing the evolution of enzymatic activity of various liquid detergent compositions, as a function of time.
Description détaillée d'une forme d'exécution préférée de l'invention [0030] La demanderesse a découvert que, de manière inattendue, l'usage de matières premières renouvelables (MPR) avait un effet stabilisant sur les enzymes, et que les performances de nettoyage étaient améliorées par rapport à une formulation connue. Parmi les performances des formulations, on compte l'effet détergent, l'effet germicide, et l'activité anti-fongique. [0031] Dans le cadre de l'invention, les activités enzymatiques, et leur stabilité au cours du temps ont été mesurées de la manière suivante : On met un substrat spécifique en présence de l'enzyme. Ce substrat est hydrolyse en un produit absorbant la lumière à une longueur d'onde de 405 nm. On mesure l'absorbance d'un échantillon de ce substrat, au moyen d'un spectrophotomètre Thermospectronic. L'absorbance mesurée permet de déduire la concentration en produit d'hydrolyse du substrat (loi de Beer- Lambert), et la variation d'absorbance ΔA/min est proportionnelle à l'activité de l'enzyme considérée. [0032] Les alkylpolyglucosides (en abrégé : APG) sont des composés de formule générale :DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT OF THE INVENTION [0030] The applicant has discovered that, unexpectedly, the use of renewable raw materials (MPR) has a stabilizing effect on the enzymes, and that the performance of cleaning were 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 concentration of hydrolysis product of the substrate (Beer-Lambert law), and the variation of absorbance ΔA / min is proportional to the activity of the enzyme in question. The alkylpolyglucosides (abbreviated as APG) are compounds of general formula:
R-O-(G)x où R est une chaîne alkyle linéaire ou branchée, et G est un monosaccharide tel que le glucose. Ces composés sont obtenus à partir d'un alcool gras issu d'une huile végétale et du monosaccharide. Parmi les APG utilisés communément et disponibles commercialement figurent les alcools gras en C8 à C16 glucosides (ci après appelé C8-C18 glucoside) tels que le cocoglucoside et les alcools gras en C12 à C16 glucoside (ci après appelé C12-C18 glucoside) tels que le laurylglucoside.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.
[0033] Dans le tableau suivant, la formulation A est une formulation classique constituée d'alcool gras éthoxylé, d'acide borique, d'éther de glycol (Dipropylène glycol monométhyl éther), d'enzymes (lipase) et de conservateurs. La formulation B est une formulation suivant l'invention, dans laquelle l'alkylpolyglucoside est un C8-C16 glucoside, l'éther de glycol est le dipropylène glycol monométhyl éther, l'huile essentielle est le terpène d'orange et l'enzyme est une lipase. On a mesuré l'activité de la lipase après un délai d'attente de 1 à 90 jours. Les résultats de ces mesures montrent que l'activité enzymatique décroît très sensiblement moins vite dans la formulation B suivant l'invention que dans la formulation A classique, l'activité étant, en moyenne, 35% supérieure dans la formulation B.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.
Figure imgf000008_0001
[0034] Des essais ont été effectués avec les formulations A et B ci- dessus, sous forme diluée. La forme diluée dans l'eau est intéressante car elle permet une utilisation sous forme de spray.
Figure imgf000008_0001
Tests were carried out with the formulations A and B above, in diluted form. The diluted form in water is interesting because it allows use as a spray.
Figure imgf000009_0001
Figure imgf000009_0001
Ces résultats montrent que les formulations enzymatiques classiques ne sont pas livrables sous forme diluée, car elles perdent pratiquement toute activité enzymatique, et doivent donc être diluées au moment de leur utilisation.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.
Effet germicide et détergentGermicidal effect and detergent
[0035] On a comparé les effets germicide et détergent de quatre formulations :The germicidal and detergent effects of four formulations were compared:
(1 ) Blanc : eau de ville(1) White: city water
(2) Produit classique : Alcool gras éthoxylé + Potasse caustique + Phosphate + Conservateurs(2) Classic product: Ethoxylated fatty alcohol + Caustic potash + Phosphate + Preservatives
(3) Produit enzymatique classique: Alcool gras éthoxylé + Acide borique + Ether de glycol (Dipropylène glycol monométhyl éther) + Enzymes (Lipase) + Conservateurs(3) Conventional enzymatic product: Ethoxylated fatty alcohol + Boric acid + glycol ether (Dipropylene glycol monomethyl ether) + Enzymes (Lipase) + Preservatives
(4) Produit enzymatique suivant l'invention, stabilisée par des MPR : C8- C16 glucoside + Ether de glycol (Dipropylène glycol monométhyl éther)(4) Enzymatic product according to the invention, stabilized by MPR: C8-C16 glucoside + glycol ether (Dipropylene glycol monomethyl ether)
+ 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 :+ Orange Terpene + Enzymes (Lipase) whose compositions are given in the table below, in which the concentrations are expressed as a percentage of the volume:
Figure imgf000009_0002
Figure imgf000009_0002
Figure imgf000010_0001
Figure imgf000010_0001
La performance d'un nettoyage peut être évaluée sur deux facteurs :The performance of a cleaning can be evaluated on two factors:
- 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.- DE (detergent effect): it reflects the degree of removal of organic soil from the surface. Its scale varies from 0 to 4. The higher its value, the higher the level of cleanliness of the surface.
- 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 (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 following table and FIG. 1 include the DE and GE values after a surface cleaning using the four formulations described:
Figure imgf000011_0001
Figure imgf000011_0001
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. Activité antifongique [0036] Des essais d'activité antifongiques ont été effectués suivant le mode opératoire suivant : Une composition suivant l'invention contient les composants suivants :In Figure 1, one dot 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 [0036] Antifungal activity tests were carried out according to the following procedure: A composition according to the invention contains the following components:
- des agents tensioactifs issus de matières premières renouvelables,surfactants derived from renewable raw materials,
- des huiles essentielles pures issues de plantes (indiquées dans le tableau ci-après par h.e. de ...)- pure essential oils from plants (indicated in the table below by h.e. of ...)
- un éther de glycol, le dipropylène glycol monométhyl éther,a glycol ether, dipropylene glycol monomethyl ether,
- des enzymes.- enzymes.
La composition détaillée est donnée dans le tableau ci-après: The detailed composition is given in the table below:
Figure imgf000012_0001
Figure imgf000012_0001
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:This composition is particularly suitable for eliminating and preventing the appearance of molds, for example in bathrooms. Operating mode:
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 :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 : champignons récoltés dans un endroit humide- inoculum: mushrooms harvested in a damp place
- 200 μl de produit est versé sur l'endroit inoculé- 200 μl of product is poured on the inoculated place
- incubation durant 48 heures à 350C Résultats:incubation for 48 hours at 35 ° C. Results:
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.Figure 2a shows the development of the mold culture after 24 hours on an untreated support. Figure 2b shows the same result, with the composition above. 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.
[0037] La demanderesse a découvert que les compositions suivant l'invention, comportant un APG, une huile essentielle, un éther de glycol, et une enzyme présentent des caractéristiques intéressantes inattendues. Pour mettre en évidence cet effet synergique, on a comparé le développement de moisissures dans des boites de pétri non traitées (ci après dénommées « blanc ») et des compositions d'essai. Les essais suivants on été effectués avec les compositions suivantes: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:
(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%).(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%).
(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%)(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%)
(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%),(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%),
(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).(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).
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 350C durant 72 heures et comparées à un blanc. Les résultats suivants sont observés : [0038] Une première série d'essais vise à évaluer l'effet antifongique de chacun des composants des compositions suivant l'invention. Les produits A, B, C et D, décrits ci-dessus, sont comparés. La figure 3a montre l'état de développement de la moisissure à l'instant initial. La figure 3b montre l'état de développement de la moisissure après 24 heures. On observe que le mycélium de la moisissure commence à s'étendre de manière circulaire à partir de l'endroit où le contaminant a été déposé. Dans la boîte où les compositions A et B ont été appliquées, aucun développement de la moisissure n'est constaté.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. Petri dishes are incubated at 35 0 C for 72 hours and compared to a blank. The following results are observed: [0038] A first series of tests aims at evaluating 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. Figure 3a shows the state of development of the mold at the initial time. 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.
La figure 3c montre l'état de développement de la moisissure après 48 heures. Après 48 heures d'incubation, la moisissure du blanc a triplé sa surface de couverture à partir de l'endroit d'inoculation de départ. Quelques points de développement de moisissures sont à constater pour le produit A, contenant une huile essentielle et le produit B, contenant une enzyme, mais ce développement est limité.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.
La figure 3c montre l'état de développement de la moisissure après 72heures. Après 72 heures d'incubation, le mycélium constitutif de la moisissure du blanc s'est encore étendu. Les points de moisissures pour le produit A et B se sont développés mais la quantité de mycélium par rapport au blanc est restreint. De plus les moisissures ne se développent pas à partir de l'endroit d'inoculation (au centre) mais plutôt à partir de la périphérie, ce qui indique la présence d'une zone d'inhibition déclenchée par l'activité antifongique des deux produits A et B. [0039] Une seconde série d'essais vise à évaluer l'effet antifongique de chacun deux types huiles essentielles utilisées dans des compositions suivant l'invention et compare les compositions C et D et le « blanc ». La figure 4a montre l'état de développement de la moisissure à l'instant initial.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, which indicates the presence of an inhibition zone triggered by the antifungal activity of the two products A and B. [0039] A second series of tests aims at evaluating the effect antifungal of each two types essential oils used in compositions according to the invention and compares the compositions C and D and the "white". Figure 4a shows the state of development of the mold at the initial time.
La figure 4b montre l'état de développement de la moisissure après 24 heures. Après 24 heures d'incubation, la moisissure commence à se développer pour le blanc. Il n'y a aucun développement pour les boîtes de pétri contenant les compositions C et D.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.
La figure 4c montre l'état de développement de la moisissure après 48 heures d'incubation. Le mycélium contenu dans le blanc a pris une ampleur considérable. On commence à apercevoir un léger développement de la moisissure pour les compositions C et D mais ce développement est beaucoup moins prononcé que pour le blanc. Ce développement moins important témoigne de l'activité antifongique des compositions C et D. La figure 4d montre l'état de développement de la moisissure après une semaine d'incubation. Après une semaine, le mycélium de la moisissure a rempli complètement toute la surface du témoin. La surface des milieux où les compositions C et D ont été déposées n'est toujours pas recouverte entièrement. De plus, le développement de moisissures est moins prononcé du côté de la composition C que de la composition D. Cela est tout à fait normal car les huiles essentielles à base d'aromates (girofle, palmarosa.etc.) sont reconnues pour leur pouvoir bactéricide et anti-fongique. Les huiles essentielles à base d'agrumes (citron, bergamote, etc..) ont quant à elle un pouvoir bactéricide et anti-fongique moins prononcé. [0040] On conclut de ces essais, d'une part, que les enzymes et les huiles essentielles (issues d'aromates) ont chacune une activité anti-fongique. Ces deux types de matières premières renouvelables peuvent donc fonctionner en synergie car elles ont des modes d'action différents sur les microorganismes. Ces résultats mettent en évidence un effet antifongique des enzymes utilisées dans les formulations de l'invention. Ensuite, le choix du mélange d'huiles essentielles détermine l'efficacité à plus ou moins long terme de l'activité anti-fongique.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 significant development is indicative of the antifungal activity of compositions C and D. Figure 4d shows the state of development of 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 in the composition C than in the composition D. This is quite normal because the essential oils based on herbs (clove, palmarosa.etc.) Are recognized for their power. bactericidal and anti-fungal. The citrus-based essential oils (lemon, bergamot, etc.) have a lower bactericidal and anti-fungal potency. It is concluded from these tests, on the one hand, that the 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.
Effet détergentDetergent effect
[0041] On a cherché à évaluer l'efficacité des constituants entrant dans les compositions suivant l'invention, pris isolément, en les comparant à un produit usuel. L'expérience consiste à enduire une coupelle en verre d'une quantité fixe de beurre coloré en rouge. Le produit à tester est mis en contact avec la coupelle, sans agitation, dans le but de vérifier l'efficacité dégraissante de la formule.It was sought to evaluate the effectiveness of the constituents entering the compositions of the invention, taken in isolation, by comparing them to 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.
Dans une première série d'essais, dont les résultats sont représentés à la figure 5, on a comparé l'effet dégraissant d'un C8-C16 glucoside, qui est un agent tensioactif utilisé dans les compositions de l'invention, avec celle d'un alcool gras éthoxylé C12-C13, 8OE, produit issu de la pétrochimie, qui est un agent tensioactif communément utilisé dans les compositions détergentes, à différentes concentrations. Ces deux agents tensioactifs de test ont été sélectionnés comme étant des agents tensioactifs efficaces, issus d'une part d'une origine végétale, et d'autre part de la pétrochimie. Les résultats de l'expérience, représentés à la figure 5, montrent que ces deux tensioactifs sont efficaces, avec un effet sensiblement meilleur pour le tensioactif d'origine végétale, particulièrement aux concentrations plus élevées, de 0,6 à 1%. Dans une seconde série d'essais, non représentés, on a comparé l'efficacité de plusieurs solvants. Les résultats de cette seconde série d'essais sont les suivants:In a first series of tests, the results of which are shown in FIG. 5, the degreasing effect of a C8-C16 glucoside, which is a surfactant used in the compositions of the invention, 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, shown in FIG. 5, show that these two surfactants are effective, with a substantially better effect for the surfactant of plant origin, 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:
- 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 :the solvents having 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:
- 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.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.
[0042] On a également cherché à mettre en évidence l'efficacité des compositions suivant l'invention, comportant un alkylpolyglucoside, une huile essentielle, un éther de glycol et une enzyme par rapport aux deux classes de produits connus de l'art antérieur. L'expérience consiste à enduire une coupelle en verre d'une quantité fixe et connue de beurre coloré en rouge. La composition à tester est mise en contact avec la coupelle, sans agitation, dans le but de vérifier l'efficacité de la formule. On verse 50 ml d'une solution à 10% de la composition à tester dans la coupelle, on laisse agir pendant 40 minutes à température ambiante, puis on étuve à 1050C pendant 20 minutes pour éliminer toute trace d'eau, et on pèse pour déterminer la quantité de beurre coloré éliminée. Les compositions suivant l'invention, MPRF1 à MPRF6, sont comparées à des produits de la première classe, le produit « Reatout » de la demanderesse, et une formulation représentative de cette classe de produits, et à des produits de la deuxième classe, le produit « Soft » de la demanderesse, et une formulation représentative de cette autre classe de produits. Les compositions des produits Reatout et Soft sont les suivantes :It was also 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 known products of 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 dish, 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:
Figure imgf000017_0001
Les compositions des produits représentatifs des premières et deuxièmes classes sont les suivantes :
Figure imgf000017_0001
The compositions of the representative products of the first and second classes are as follows:
Figure imgf000018_0001
Figure imgf000018_0001
5 L'efficacité de chacune des formulations, déterminée comme étant le pourcentage en poids de beurre coloré éliminé, sont données dans le tableau ci-après :The effectiveness of each of the formulations, determined as the percentage by weight of colored butter removed, is given in the table below:
Figure imgf000018_0002
Figure imgf000019_0001
Figure imgf000018_0002
Figure imgf000019_0001
La figure 6 représente l'évolution après 1 h de trempage. On voit que la composition suivant l'invention MPR5 (figure 6 a) est plus efficace en pouvoir dégraissant que des produits du marché de classe 1 (figure 6 b) et 2 (figure 6 c). Cette amélioration du pouvoir dégraissant d'une compositions suivant l'invention peut être expliquée par la synergie de l'action des enzymes (lipase) et des autres composants du produit (C8-C16 glucoside, éther de glycol, huiles essentielles).Figure 6 shows the evolution after 1 hour of soaking. It can be seen that the composition according to the invention MPR5 (FIG. 6 a) is more effective in degreasing power than products of the class 1 market (FIG. 6b) and 2 (FIG. 6c). 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).
Utilisation sous forme de sprayUse as a spray
[0043] On a également cherché à mettre en évidence l'efficacité d'une composition suivant l'invention utilisable sous forme spray, c'est-à-dire une composition fortement diluée à l'eau, comportant un alkylpolyglucoside, une huile essentielle, un éther de glycol et une enzyme. L'efficacité de cette composition est comparée avec celle d'une formulation nettoyant spray multi usages représentative de ce qui existe sur le marché. Les compositions de ces deux formulations et leur efficacité, déterminée comme étant le pourcentage en poids de beurre coloré éliminé, sont détaillées dans le tableau ci-après :It has also been sought to demonstrate the effectiveness of a composition according to the invention that can be used in spray form, that is to say a composition which is strongly diluted with water, comprising an alkylpolyglucoside, an essential oil. , a glycol ether 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:
Figure imgf000020_0001
Figure imgf000020_0001
Le test est également réalisé dans des coupelles en verre recouvertes d'une fine couche de beurre coloré à l'aide d'un colorant rouge. Une quantité de 0,5 g de beurre par coupelle est étalé uniformément sur toute la surface. Les compositions à tester sont mises en contact avec les coupelles, sans agitation, dans le but de vérifier l'efficacité de la formule. On verse 50 ml d'une solution pure de chaque composition à tester dans la coupelle. Ce test d'efficacité se réalise sans action mécanique et à température ambiante. Les résultats sont observés après 40 minutes (voir figure 7). Dès les premières minutes, le spray suivant l'invention (figure 7b) attaque la matière grasse alors que le produit du marché (figure 7a) n'agit presque pas. Après 40 minutes, une plus grande quantité de la matière grasse a été décollée par le spray suivant l'invention alors qu'une quantité importante de matière grasse est encore présente sur la coupelle traitée au moyen du produit du marché. De plus, le spray de l'invention émulsionne beaucoup mieux la matière grasse que le produit du marché. La variation de pH, avant et après action du produit, pour la composition suivant l'invention est de 0,27, alors qu'elle est nulle pour le produit du marché. L'émulsion obtenue avec le spray suivant l'invention s'est donc acidifiée. Ceci indique que les lipases contenues dans la formulation ont bien agi sur les triglycérides en transformant une partie de la matière grasse en acides gras, entraînant l'acidification du mélange. En définitive, le nouveau spray suivant l'invention, à base de MPR est, a des propriétés améliorées par rapport aux produits du marché. Grâce à ses éléments naturels puissants fonctionnant de manière synergique (C8-C16 glucoside, terpène d'orange, lipase), il parvient à s'attaquer aux matières grasses efficacement et rapidementThe 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 (FIG. 7b) attacks the fat while the product of the market (FIG. 7a) hardly acts. 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
Stabilité des enzymesStability of enzymes
[0044] On a enfin cherché à mettre en évidence les caractéristiques de stabilité des enzymes dans diverses formulations. La figure 8 représente l'évolution des activités enzymatiques des compositions suivant l'invention MPRF1 à MPRF6, et d'une composition enzymatique classique, sans MPR, le produit « Degrés L » de la demanderesse. On constate que dans tous les cas, l'activité enzymatique des compositions suivant l'invention est supérieure à celle de la composition « Degrés L ». On a également testé la stabilité de l'enzyme dans diverses formulations reprises dans le tableau ci-après. MPR1 ne contient ni huile essentielle, ni éther de glycol. Dans MPR2, on a ajouté un éther de glycol : le dipropylèneglycol monométhyl éther. Dans MPR3, un terpène est présent, mais pas d'éther de glycol. Dans MPR4, il n'y a pas de MPR. MPR5 est une composition suivant l'invention. MPR6 est comparable à MPR1 , mais l'agent tensioactif est un produit commercial issu de l'industrie pétrochimique. MPR7 contient un éther de glycol et une enzyme.Finally, we sought to highlight the stability characteristics of the enzymes in various formulations. FIG. 8 represents the evolution of the enzymatic activities of the compositions according to the invention MPRF1 to MPRF6, and of a conventional enzymatic composition, without MPR, the product "Degrees 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.
Figure imgf000022_0001
Figure imgf000022_0001
La figure 9 représente l'évolution des activités enzymatiques de ces compositions. On constate que le terpène d'orange (composition MPR4) et un C8-C16 glucoside (composition MPR1 ) sont deux MPR qui stabilisent très fortement l'enzyme. On constate également que le dipropylèneglycol monométhyl éther (composition MPR7) donne une meilleure stabilité que l'alcool gras éthoxylé C12-C13, 8OE (composition MPR6). L'éther de glycol est présent dans la formulation car son rôle dégraissant est indispensable. Enfin, il est important de remarquer que l'activité enzymatique obtenue avec une composition contenant un tensioactif 100% végétal (C8-C16 glucoside : MPR1) est meilleure que celle obtenue avec un tensioactif 100% pétrochimique (alcool gras éthoxylé C12-C13, 8OE: MPR7). Figure 9 shows the evolution of 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

REVENDICATIONS
1. Composition détergente liquide comprenant (a) de 1 à 30 % en volume d'un alkylpolyglucoside,A liquid detergent composition comprising (a) from 1 to 30% by volume of an alkylpolyglucoside,
(b) de 0,01 à 3 % en volume d'une huile essentielle,(b) from 0.01 to 3% by volume of an essential oil,
(c) de 0,1 à 20 % en volume d'un éther de glycol,(c) from 0.1 to 20% by volume of a glycol ether,
(d) de 0,01 à 10 % en volume d'une enzyme, le complément à 100% en volume étant constitué principalement d'eau. (d) from 0.01 to 10% by volume of an enzyme, the 100% by volume supplement consisting mainly of water.
2. Composition suivant la revendication 1 caractérisée en ce que l'alkylpolyglucoside est choisi parmi le groupe consistant en un C8-C16 glucoside, un C12-C16 glucoside , et leurs mélanges.2. Composition according to claim 1 characterized in that the alkylpolyglucoside is selected from the group consisting of a C8-C16 glucoside, a C12-C16 glucoside, and mixtures thereof.
3. Composition suivant l'une quelconque des revendications précédentes caractérisée en ce que l'huile essentielle est choisie parmi le groupe consistant en le terpène d'orange, les huiles essentielles obtenues à partir du citrus limonum, du citrus aurantium L., du citrus aurantium L. ssp. bergamia, du cymbopogon martinii, du Thymus vulgaris, et leurs mélanges.3. Composition according to any one of the preceding claims, characterized in that the essential oil is 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.
4. Composition suivant l'une quelconque des revendications précédentes caractérisée en ce que l'éther de glycol est choisi parmi le groupe consistant en le dipropylène glycol monométhyl éther, le propylène glycol monométhyl éther, et leurs mélanges.4. Composition according to any one of the preceding claims characterized in that the glycol ether is selected from the group consisting of dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, and mixtures thereof.
5. Composition suivant l'une quelconque des revendication précédentes caractérisée en ce que l'enzyme est choisi parmi5. Composition according to any one of the preceding claims, characterized in that the enzyme is chosen from
- les lipases, - les protéases,lipases, proteases,
- les cellulases,cellulases,
- les hémicellulases,hemicellulases,
- les amylases,amylases,
- les β-glucanases, - les xylanases,β-glucanases, xylanases,
- les arabanases et leurs mélanges. arabanases and their mixtures.
6. Composition suivant l'une quelconque des revendication précédentes caractérisée en ce que la teneur en alkylpolyglucoside est comprise entre 10% et 20% en volume.6. Composition according to any one of the preceding claims, characterized in that the content of alkylpolyglucoside is between 10% and 20% by volume.
7. Composition suivant l'une quelconque des revendication précédentes caractérisée en ce que la teneur en l'huile essentielle est comprise entre 1 % et 2% en volume.7. Composition according to any one of the preceding claims characterized in that the content of the essential oil is between 1% and 2% by volume.
8. Composition suivant l'une quelconque des revendication précédentes caractérisée en ce que la teneur en éther de glycol est comprise entre 5% et 15% en volume. 8. Composition according to any one of the preceding claims characterized in that the content of glycol ether is between 5% and 15% by volume.
9. Composition suivant l'une quelconque des revendication précédentes caractérisée en ce que la teneur en l'enzyme est comprise entre 1% et 3% en volume.9. Composition according to any one of the preceding claims, characterized in that the content of the enzyme is between 1% and 3% by volume.
10. Composition suivant l'une quelconque des revendication précédentes, pour utilisation sous forme de spray, caractérisée en ce que la teneur en eau est comprise entre 85% et 97% en volume.10. Composition according to any one of the preceding claims, for use in the form of a spray, characterized in that the water content is between 85% and 97% by volume.
11. Utilisation d'une composition suivant l'une quelconque des revendication précédentes sous forme de spray.11. Use of a composition according to any one of the preceding claims in spray form.
12. Utilisation suivant la revendication 11 dans un but antifongique. Use according to claim 11 for antifungal purpose.
PCT/EP2006/060244 2006-02-23 2006-02-23 Liquid detergent composition containing an enzyme WO2007095999A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
ES06708495T ES2329931T3 (en) 2006-02-23 2006-02-23 COMPOSITION DETERGENT LIQUID CONTAINING AN ENZYME.
DE602006007880T DE602006007880D1 (en) 2006-02-23 2006-02-23 LIQUID DETERGENTS WITH ENZYME
PCT/EP2006/060244 WO2007095999A1 (en) 2006-02-23 2006-02-23 Liquid detergent composition containing an enzyme
EP06708495A EP1987125B1 (en) 2006-02-23 2006-02-23 Liquid detergent composition containing an enzyme

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2006/060244 WO2007095999A1 (en) 2006-02-23 2006-02-23 Liquid detergent composition containing an enzyme

Publications (1)

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WO2007095999A1 true WO2007095999A1 (en) 2007-08-30

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Country Status (4)

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EP (1) EP1987125B1 (en)
DE (1) DE602006007880D1 (en)
ES (1) ES2329931T3 (en)
WO (1) WO2007095999A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2627752A1 (en) * 2010-10-15 2013-08-21 Realco SA Product and method for the removal of biofilms
EP2627747A1 (en) * 2010-10-15 2013-08-21 Realco SA Product and method for the removal of biofilms
BE1025146B1 (en) * 2017-09-22 2018-11-13 Realco Composition comprising an enzymatic component and a detergent component
EP3418359A1 (en) * 2017-06-22 2018-12-26 The Procter & Gamble Company Cleaning product
BE1027322A1 (en) 2019-05-29 2021-01-05 Realco Cleaning and degreasing composition for the treatment of hard surfaces
US11124739B2 (en) 2017-06-22 2021-09-21 The Procter & Gamble Company Cleaning product
US11180715B2 (en) 2017-06-22 2021-11-23 The Procter & Gamble Company Sprayable cleaning composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4134423A1 (en) * 2021-08-12 2023-02-15 Henkel AG & Co. KGaA Sprayable laundry pre-treatment composition

Citations (3)

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Publication number Priority date Publication date Assignee Title
WO1994025561A1 (en) * 1993-05-05 1994-11-10 Novo Nordisk A/S Cleaning gel
EP0798371A1 (en) * 1996-03-29 1997-10-01 The Procter & Gamble Company Detergent compositions comprising specific amylase and alkyl poly glucoside surfactants
US6136778A (en) * 1998-07-22 2000-10-24 Kamiya; Akira Environment safeguarding aqueous detergent composition comprising essential oils

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994025561A1 (en) * 1993-05-05 1994-11-10 Novo Nordisk A/S Cleaning gel
EP0798371A1 (en) * 1996-03-29 1997-10-01 The Procter & Gamble Company Detergent compositions comprising specific amylase and alkyl poly glucoside surfactants
US6136778A (en) * 1998-07-22 2000-10-24 Kamiya; Akira Environment safeguarding aqueous detergent composition comprising essential oils

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2627752A1 (en) * 2010-10-15 2013-08-21 Realco SA Product and method for the removal of biofilms
EP2627747A1 (en) * 2010-10-15 2013-08-21 Realco SA Product and method for the removal of biofilms
EP2627747B1 (en) * 2010-10-15 2016-09-14 Realco SA Method for the removal of biofilms
EP3418359A1 (en) * 2017-06-22 2018-12-26 The Procter & Gamble Company Cleaning product
US11124739B2 (en) 2017-06-22 2021-09-21 The Procter & Gamble Company Cleaning product
US11180715B2 (en) 2017-06-22 2021-11-23 The Procter & Gamble Company Sprayable cleaning composition
BE1025146B1 (en) * 2017-09-22 2018-11-13 Realco Composition comprising an enzymatic component and a detergent component
BE1027322A1 (en) 2019-05-29 2021-01-05 Realco Cleaning and degreasing composition for the treatment of hard surfaces
BE1027322B1 (en) * 2019-05-29 2021-01-12 Realco Cleaning and degreasing composition for the treatment of hard surfaces

Also Published As

Publication number Publication date
EP1987125B1 (en) 2009-07-15
DE602006007880D1 (en) 2009-08-27
ES2329931T3 (en) 2009-12-02
EP1987125A1 (en) 2008-11-05

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