WO1996004342A1 - Cleaning or scouring compositions, and preparations containing them - Google Patents

Cleaning or scouring compositions, and preparations containing them Download PDF

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Publication number
WO1996004342A1
WO1996004342A1 PCT/FR1995/000994 FR9500994W WO9604342A1 WO 1996004342 A1 WO1996004342 A1 WO 1996004342A1 FR 9500994 W FR9500994 W FR 9500994W WO 9604342 A1 WO9604342 A1 WO 9604342A1
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WO
WIPO (PCT)
Prior art keywords
solvent
composition according
surfactant
glycol
weight
Prior art date
Application number
PCT/FR1995/000994
Other languages
French (fr)
Inventor
Michel Michallet
Original Assignee
Ste Industrielle Et Commerciale Du Rhone - Sincora
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 Ste Industrielle Et Commerciale Du Rhone - Sincora filed Critical Ste Industrielle Et Commerciale Du Rhone - Sincora
Priority to AU30820/95A priority Critical patent/AU3082095A/en
Priority to EP95926421A priority patent/EP0773978A1/en
Publication of WO1996004342A1 publication Critical patent/WO1996004342A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D9/00—Chemical paint or ink removers
    • C09D9/04—Chemical paint or ink removers with surface-active agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to the field of cleaning agents such as detergents and strippers, and in particular compositions in the form of a stable emulsion or microemulsion, intended to remove undesirable coatings of variable chemical constitution, paint type, and / or dirt, in particular strongly encrusting, deposited on various types of support surfaces, for example application materials or the skin.
  • cleaning agents such as detergents and strippers
  • compositions in the form of a stable emulsion or microemulsion intended to remove undesirable coatings of variable chemical constitution, paint type, and / or dirt, in particular strongly encrusting, deposited on various types of support surfaces, for example application materials or the skin.
  • compositions of the invention can be used to remove single-component or two-component paints that are not yet crosslinked or else crosslinked, sealants, glues, primers, inks, applied in layers or accidentally sprayed or no, on hard substrates' such as floors, walls, but also the bodies, and on plastics and composites more fragile media and on the skin, especially the hands.
  • compositions must be particularly effective, while preserving the cleaned support intact. They must have a low harmfulness for the manipulator, must meet the requirements of standards such as those regulating the use of cleansing creams for the skin, and must have a viscosity such that their action can be exerted as well in horizontal application as vertical .
  • a cleaning composition in the form of an emulsion, comprising, as active ingredient, a solvent fraction or internal phase chosen from dibasic esters, having a power solvent with respect to resins, water as an external phase, and an agent thickener, giving the composition stability of the emulsion and thixotropy.
  • the Applicant provides a cleaning and / or stripping composition, in the form of an emulsion constituted by an internal phase dispersed in an external phase, not having the drawbacks described above.
  • the subject of the present invention is in particular a composition containing little or no thickening agent.
  • thickener an adjuvant whose contribution makes it possible to adjust the viscosity of the composition, of the type chosen from among the gums such as xanthan gums, alginates, polyvinyl alcohols, polyacrylates, starches, derived from clays and cellulose, such as hydroxypropyl-methyl-cellulose. It is understood that none of the constituents revealed by the present description for obtaining the compositions of the invention can be considered as a thickener within the meaning of this definition.
  • a composition according to the invention comprises at least one solvent fraction comprising at least one solvent, that is to say a solvent or a mixture of solvents and at least one cosolvent, that is to say a cosolvent or a mixture cosolvents, and a surfactant fraction, in the form of an emulsion stable over time, in particular retaining its flexibility, non or slightly harmful, low flammability and biodegradable.
  • An emulsion is formed by the dispersion of a so-called internal phase in a so-called continuous external phase;
  • a microemulsion consists of an internal phase in the form of microdroplets of size 10 to 100 times smaller than the droplets of an emulsion defined above;
  • the internal phase according to the invention is the active solvent phase with respect to at least one resin, comprising at least one active solvent, and optionally at least one co-solvent;
  • the external phase is the continuous phase of the emulsion, aqueous or non-aqueous, which may comprise at least one cosolvent;
  • a cosolvent is a solvent having non-solvent activity with respect to at least one resin, making it possible to adjust the specific solvent power of the solvent fraction containing it; this cosolvent may itself be soluble or not in the external phase;
  • composition with low flammability is understood to mean a composition whose flash point in open section is greater than 50 ° C., and preferably whose flash point is greater than or equal to 100 ° C.
  • a cleaning composition not very aggressive, both vis-à-vis the user or the environment, easily removable, stable and practically non-volatile, could be obtained, on the one hand by adjusting with a cosolvent the solvent power of the solvent fraction, and on the other hand by using jointly with the solvent fraction thus determined specific surfactants.
  • the solvent fraction is defined in Hansen space by its partial parameter of polarity ⁇ p and its parameter partial connecting .DELTA.h hydrogen, inside of a parallelepiped whose projection in the plane Ap, .DELTA.h is a rectangular area having a length on the .DELTA.h axis 16 (cal / cm 3) 1/2, or 32, 64 (J / cm 3) 1/2 from the point of origin 0, and a width on the axis Ap of 12 (cal / cm 3) 1/2, or 24.48 (J / cm 3) 1 / 2 from the point of origin 0, the value of the partial dispersion parameter ⁇ d not being limiting, and on the other hand, said surfactant fraction comprises at least one main nonionic surfactant chosen from alcohols, acids and ethoxylated or non-ethoxylated fatty esters, the long linear, saturated, hydrophobic carbon chain of which has at least 18 carbon atoms, and in particular 18 carbon atom
  • main surfactant is intended to mean an essential surfactant in the compositions described and the proportion by weight of which is not necessarily the majority in these compositions.
  • said main nonionic surfactant is itself defined in the Hansen space by its partial parameter of polarity ⁇ p and its partial hydrogen bonding parameter ⁇ h, inside the same parallelepiped as that determined above for the solvent fraction. .
  • the partial hydrogen bonding parameter ⁇ h of said main nonionic surfactant is greater than 3 (cal / cm 3 ) , 2 , or 6.12 (J / cm 3 ) 72 , or better still he is between 3 (cal / cm 3 ) 1/2 , or 6.12 (J / cm 3 ) 1/2 , and 8 (cal / cm 3 ) 1/2 , or 16.32 (J / cm 3 ) l2 , and its partial polarity parameter ⁇ p is less than 3 (cal / cm 3 ) 1/2 , or 6.12 (J / cm 3 ) ' / 2 .
  • Said main nonionic surfactant is advantageously present in the composition in a weight concentration of between 1 and 15% of the total weight of the composition.
  • this main nonionic surfactant is chosen from glycerol mono- and distearate, ethylene glycol mono- and distearate, diethylene glycol mono- and distearate and mono- and propylene glycol distearate, and ethoxylated stearyl alcohol with an ethoxylation index of between 2 and 21, and any mixture thereof.
  • the external fraction ' is also defined in Hansen space by its partial polarity parameter ⁇ p and its partial hydrogen bonding parameter ⁇ h, inside the same parallelepiped as that determined for the solvent fraction, that is i.e. a parallelepiped whose projection in the plane ⁇ p, ⁇ h is a rectangular surface having a length on the axis ⁇ h of 16 (cal / cm 3 ) l2 , or 32.64 (J / cm 3 ) l / 2 , from the point of origin 0, and a width on the axis ⁇ p of 12 (cal / cm 3 ) 1/2 , or 24.48 (J / cm 3 ) / 2 , from the point of origin 0.
  • the partial parameters ⁇ p and ⁇ h of solubility of the external phase have values between 0 and 10 (cal / cm 3 ) 72 , or 20.4 (J / cm 3 ) l2 , for its partial parameter polarity ⁇ p, and between 3.5 (cal / cm 3 ) , 2 , or 7.14 (J / cm 3 ) , / 2 , and 16 (cal / cm 3 ) 12 , or 32.64 (J / cm 3 ) l / 2 , for its partial hydrogen bonding parameter ⁇ h, the values of its partial dispersion parameter ⁇ d being preferably chosen between 7 (cal / cm 3 ) Vl , or 14.28 (J / cm 3 ) ' / 2 , and 10 (cal / cm 3 ) '72 , i.e.
  • compositions of the invention make it possible to exploit the properties of the solvent fraction to the maximum, while being able to involve low concentrations of the latter.
  • compositions having a versatile activity that is to say capable of acting on different coatings and soiling, or else very selective compositions acting specifically on such coatings or soiling.
  • said cosolvent will be chosen as a function of the reciprocal solubilities of the solvent and of the cosolvent, as well as of their respective solubilities in water.
  • the solvent is chosen from dialkylesters, such as mixtures of adipate, glutarate and succinate of the RPDE® type (marketed by the company Rhône-Poulenc) and DBE® (marketed by the company Dupont de Nemours), but also dibutylphthalate, among monoalkylesters such as ethyl lactate, butyl lactate and other lactic acid esters, propylene carbonate, ethylene carbonate, among ethylene glycol ether esters , esters of propylene glycol ethers, such as propylene glycol methyl acetate, propylene glycol diacetate, methoxy esters and ethoxy esters such as ethyl 3-propionate (abbreviated as EEP), among ethers of ethylene glycol and ethers of prop
  • dialkylesters such as mixtures of adipate, glutarate and succinate of the RPDE® type (marketed by the company Rhône-Poulenc) and DBE® (marketed by
  • the cosolvent is advantageously chosen from glycol derivatives comprising mono-, di- and tri- and other polyethylenes and polypropylenes glycol, and hexylene glycol, from glycerol, sorbitol, dextrose and sucrose, from ethylene glycol ethers and propylene glycol ethers, soluble or moderately soluble in water, such as propylene glycol methyl ether, dipropylene glycol methyl ether and tripropylene glycol methyl ether, among aliphatic and aromatic alcohols such as benzyl alcohol, among acetone, N-methyl-2-pyrrolidone, 7-butyrolactone, as well as water, or any mixture of these.
  • glycol derivatives comprising mono-, di- and tri- and other polyethylenes and polypropylenes glycol, and hexylene glycol, from glycerol, sorbitol, dextrose and sucrose, from ethylene glycol ethers and propylene glyco
  • the solvent fraction will consist of a dimethylester or a mixture of dimethyl esters, as solvent, and the monopropylene glycol, glycerol, hexylene glycol or a polypropylene glycol of average molecular weight greater than or equal to 400, as cosolvent.
  • the weight concentration of the solvent fraction is between 1 and 90% of the total weight of the composition.
  • the surfactant fraction of the compositions of the invention also comprises at least one other surfactant, different from the main surfactant, 8
  • nonionic surfactants chosen from nonionic surfactants, anionic, photeric and cationic surfactants.
  • the other nonionic surfactant will preferably be chosen from ethoxylated fatty acids, ethoxylated fatty alcohols, ethoxylated nonylphenols, alkylpolyglucosides, ethoxylated or non-ethoxylated fatty amides, sorbitan esters or not, the alkanolamides.
  • the other anionic surfactant will preferably be chosen from alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, phosphoric esters of ethoxylated fatty alcohol.
  • amphoteric surfactant will preferably be chosen from alkylbetaine derivatives.
  • a composition of the invention comprises, as surfactant different from the main surfactant, a mixture of surfactants having a carbon chain of C 12 ⁇ c i 8 ', that is to say C 12 , C 14 ' C 16 / i 8 / with a weight proportion of surfactants in C ⁇ g-Ci ⁇ , at least equivalent to that in surfactants in C ⁇ 2 ⁇ c ⁇ -
  • composition of the invention will advantageously include:
  • a particularly advantageous washing cream of the invention has a complementary solvent power with respect to fatty substances provided by the surfactant fraction.
  • a composition of the invention comprises, as surfactant different from the main surfactant, at least one surfactant chosen from those having a carbon chain C8-C12 and which are ethoxylated with an ethoxylation index between 1 and 5, or not ethoxylated.
  • composition of the invention will advantageously include:
  • the weight concentration of the surfactant, or of surfactants other than the main surfactant, is at most equal to 50%.
  • Additives can be added to the compositions of the invention, in particular neutral, acid or alkaline, organic or mineral salts, or alternatively organic or mineral acids or bases. They may or may not be dissolved and may then be present "in any emulsion or composition according to the invention in the form of a filler such as a fine powder in suspension, which promotes the adsorption of the pigments of the resin eliminated by the composition of the 'invention. In addition, faster and more complete cleaning when rinsing the support is also obtained.
  • a filler such as a fine powder in suspension
  • FIG. 1 shows the projection in the plane ( ⁇ p, ⁇ h) of the solubility volumes according to the Hansen theory of two resins Rx and Ry, having in common a set of points;
  • FIG. 2 represents the projection in the plane ( ⁇ p, ⁇ h) of the points defined in the Hansen space of the solvent fractions Ll, L2, L3, L4, N, D, Ml, MG1, MG2, MG3, MG4, which are the subject of examples 4, 5, and 6, and points defined in the same space of pure solvents.
  • emulsions are prepared according to the direct emulsion method.
  • the surface-active constituents and the water, if this is provided as an external phase in the composition, or the component constituting the external phase of the emulsion, are heated to 70 ° C / 80 ° C and mixed perfectly.
  • the cosolvent (s) and then the solvent (s) or both are added with constant stirring. Stirring is kept constant until complete cooling during which the emulsion is formed.
  • the following fractions are classified into three categories: active, not very active (limiting action) or inactive.
  • active not very active (limiting action) or inactive.
  • the representative points of the active fractions are located inside the solubility volume of the resin studied.
  • the representative points of the inactive fractions are located on the envelope of this volume of solubility.
  • the representative points of the inactive fractions are located outside this same volume.
  • Fig 1 we represent this volume of solubility by its projection on the plane ( ⁇ p, ⁇ h), parallel to ' the axis ⁇ d.
  • point A represents a solvent fraction active on the two resins Rx and Ry.
  • Point C represents a solvent fraction active only on the resin Rx.
  • Points D and B represent two inactive solvent fractions on Rx and Ry. Each point can represent either a pure solvent or a mixture of several solvents. If point A represents a pure solvent A and point B a pure cosolvent B, by mixing A and B in suitable volume ratios, a solvent fraction C will be produced which will be active on the resin Rx and inactive on the resin Ry .
  • composition I is as follows, given as a percentage weight, the internal phase of the emulsion consisting of the solvent fraction and the external phase of water mixed with the surfactant fraction:
  • Composition I was tested on metal test plates coated with a bonding primer on which the following paints were applied:
  • the partial solubility parameters of the solvent phase of composition I correspond in FIG. 1 to a point of the type point A which is located inside the solubility volumes of the different pickled resins, and in FIG. 2, to point D .
  • compositions like composition I are certainly slower than strippers based on methylene chloride, but they have the advantage of stripping more deeply in a single operation, without evaporation and without drying. Composition I after 48 hours at 35 ° C is still flexible and perfectly rinsable with water.
  • Rx resin is a cellulosic paint with a matt black color.
  • the calculated values of ⁇ d, ⁇ p, ⁇ h for the four mixtures mentioned determine the four limit points representing four solvent fractions at the limit of action on the resin Rx which is a matt black cellulose paint, to be cleaned. These four points determine a portion of the volume of solubility of the resin Rx.
  • FIG. 2 represents the projection on the plane ⁇ p, ⁇ h of these points and of some pure solvents, the value of ⁇ d for these points being in parentheses.
  • the portion of the curve connecting the points L1, L2, L3, L4 represents the projection onto the plane ( ⁇ p, ⁇ h) of the portion of the volume of solubility of the resin Rx determined previously.
  • the points to the right of this curve represent inactive solvent fractions on the Rx resin.
  • the points to the left of this same curve represent the active solvent fractions.
  • composition of the invention to the specific cleaning of a black cellulosic paint to be removed on various types of paint to be preserved
  • composition II used is the following, given as a percentage by weight:
  • Point N in Figure 2 represents the position in Hansen space and in the plane ( ⁇ p, ⁇ h) of the solvent fraction of composition II.
  • Composition II is applied as follows:
  • a first application is made with a brush, or soft brush or soft cloth for 2 minutes; mechanical action accelerates the dissolution and emulsification of pigments in cellulosic paint
  • Composition II has an emulsified solvent fraction: a) sufficiently solvent to dissolve the cellulose paint consisting of a resin and pigments, which are emulsified and maintained in the emulsion of the composition, by the surfactant phase of the latter, and these soiling becomes easily rinsable with water b) soft enough not to alter the paint film to be restored for the time necessary for cleaning.
  • composition II is practically odorless, non-volatile, non-flammable, non-harmful, completely biodegradable, and very effective with a low concentration of active solvent (DBE® 25% w / w).
  • composition III used is the following, given as a percentage by weight:
  • the point M1 represented in FIG. 2 corresponds to a fraction of solvent with a reduced content of active solvent. But it makes it possible to remove very encrusting dirt perfectly such as paints, mastics, inks, etc.
  • compositions MG1 to MG4 were prepared, their formulations are presented in Table 4 below.
  • Glycerol mono-distearate 10 10 10 10 10 Alkyl sulfate C 12 _C 18 10 10 10 Alkyl sulfate C ⁇ gC ⁇ 2 2 2 2 2
  • Hansen's theory makes it possible to calculate the theoretical position of the solvent power of a mixture, even if it consists of at least two insoluble constituents; in this particular case, we will speak of virtual points, obtained by projection in the plane ( ⁇ p, ⁇ h).
  • the four points MG1, MG2, MG3, MG4 are virtual points.
  • the corresponding compositions MG3 and MG4 should not be active on dirt, but these four compositions are active on all paint soils and in particular on matt black cellulose paint.
  • the internal phase of the emulsion contains only emulsified DBE®.
  • This case makes it possible to engage contents of active solvent even lower than in the previous case (the difference between the four compositions lies only in the cleaning speed which decreases from MG1 to MG4).

Abstract

The invention relates to a cleaning or scouring composition in the form of an emulsion including at least one solvent fraction, comprising at least one solvent having a solvent power with respect to at least one resin, a surfactant fraction comprising at least one main non ionic surfactant, on the one hand said solvent fraction further comprising at least one co-solvent, said solvent and co-solvent being selected so that the solvent fraction is defined within the Hansen space by the partial parameter of polarity δp and the partial parameter of hydrogen bond δh, inside a parallepipede whose projection in the plane δp, δh is a rectangular surface having a length on the δh axis of 16 (cal/cm3)1/2, that is 32,64 (J/cm3)1/2, from the point of origin 0, and a width on the δp axis of 12 (cal/cm3)1/2, that is 24,48 (J/cm3)1/2, from the point of origin 0, and on the other hand said main non ionic surfactant is selected among alcohols, fatty acids and esters, ethoxylated or not, and whose long hydrophobic, saturated, linear, carbon chain has at least 18 carbon atoms.

Description

COMPOSITIONS NETTOYANTES OU DECAPANTES, ET PREPARATIONS CLEANING OR STRIPPING COMPOSITIONS, AND PREPARATIONS
LES CONTENANT L'invention relève du domaine des agents nettoyants tels que détergents et décapants, et en particulier des compositions se présentant sous la forme d'une emulsion ou d'une microémulsion stable, destinées à éliminer des revêtements indésirables de constitution chimique variable, du type peinture, et/ou des salissures, notamment fortement inscrustantes, déposées sur des surfaces de support de natures diverses, par exemple de matériels d'application ou de la peau.THE CONTAINERS The invention relates to the field of cleaning agents such as detergents and strippers, and in particular compositions in the form of a stable emulsion or microemulsion, intended to remove undesirable coatings of variable chemical constitution, paint type, and / or dirt, in particular strongly encrusting, deposited on various types of support surfaces, for example application materials or the skin.
A titre d'exemple, les compositions de l'invention sont utilisables pour supprimer des peintures à monocomposants ou à deux composants non encore réticulés ou bien réticulés, des mastics, des colles, des apprêts, des encres, appliqués en couche ou projetés accidentellement ou non, sur des supports durs' comme les sols, les murs, mais aussi les carrosseries, et sur des supports plus fragiles plastiques et composites, ainsi que sur la peau, en particulier les mains.By way of example, the compositions of the invention can be used to remove single-component or two-component paints that are not yet crosslinked or else crosslinked, sealants, glues, primers, inks, applied in layers or accidentally sprayed or no, on hard substrates' such as floors, walls, but also the bodies, and on plastics and composites more fragile media and on the skin, especially the hands.
Pour couvrir ce large spectre d'applications, de telles compositions doivent être particulièrement efficaces, tout en préservant intact le support nettoyé. Elles doivent présenter une faible nocivité pour le manipulateur, doivent répondre aux exigences de normes telles que celles réglementant l'usage des crèmes nettoyantes pour la peau, et doivent posséder une viscosité telle que leur action peut s'exercer aussi bien en application horizontale que verticale. Pour obtenir de telles propriétés, il est proposé selon EP-0 294 041, une composition nettoyante, sous forme d'emulsion, comprenant, à titre d'ingrédient actif, une fraction solvante ou phase interne choisie parmi les esters dibasiques, possédant un pouvoir solvant vis-à-vis des résines, de l'eau comme phase externe, et un agent épaississant, conférant à la composition une stabilité de 1'emulsion et une thixotropie.To cover this broad spectrum of applications, such compositions must be particularly effective, while preserving the cleaned support intact. They must have a low harmfulness for the manipulator, must meet the requirements of standards such as those regulating the use of cleansing creams for the skin, and must have a viscosity such that their action can be exerted as well in horizontal application as vertical . To obtain such properties, it is proposed according to EP-0 294 041, a cleaning composition, in the form of an emulsion, comprising, as active ingredient, a solvent fraction or internal phase chosen from dibasic esters, having a power solvent with respect to resins, water as an external phase, and an agent thickener, giving the composition stability of the emulsion and thixotropy.
Néanmoins, cette solution présente un inconvénient majeur lié à l'utilisation d'épaississants. En effet, ceux-ci, après évaporation partielle de l'eau de 1'emulsion, forment un film superficiel sec. Ce dernier d'une part n'empêche pas la poursuite de l'évaporation de l'eau, surtout lorsque la température ambiante est élevée, mais d'autre part durcit facilement et se révèle difficile à éliminer selon les supports.However, this solution has a major drawback linked to the use of thickeners. In fact, these, after partial evaporation of the water from the emulsion, form a dry surface film. The latter on the one hand does not prevent the continued evaporation of water, especially when the ambient temperature is high, but on the other hand hardens easily and proves difficult to remove depending on the media.
La demanderesse apporte une composition nettoyante et/ou décapante, sous la forme d'une emulsion constituée par une phase interne dispersée dans une phase externe, ne possédant pas les inconvénients décrits ci-dessus. La présente invention a notamment pour objet une composition ne contenant pas ou peu d'agent épaississant.The Applicant provides a cleaning and / or stripping composition, in the form of an emulsion constituted by an internal phase dispersed in an external phase, not having the drawbacks described above. The subject of the present invention is in particular a composition containing little or no thickening agent.
Par épaississant, on entend un adjuvant dont l'apport permet d'ajuster la viscosité de la composition, du type de ceux choisis parmi les gommes telles que les gommes de xanthane, les alginates, les alcools polyvinyliques, les polyacrylates, les amidons, les dérivés des argiles et de la cellulose, comme 1'hydroxypropyl-méthyl-cellulose. Il est bien entendu qu'aucun des constituants révélés par la présente description pour obtenir les compositions de l'invention, ne peut être considéré comme un épaississant au sens de cette définition.By thickener is meant an adjuvant whose contribution makes it possible to adjust the viscosity of the composition, of the type chosen from among the gums such as xanthan gums, alginates, polyvinyl alcohols, polyacrylates, starches, derived from clays and cellulose, such as hydroxypropyl-methyl-cellulose. It is understood that none of the constituents revealed by the present description for obtaining the compositions of the invention can be considered as a thickener within the meaning of this definition.
Une composition selon 1 ' invention comprend au moins une fraction solvante comprenant au moins un solvant, c'est-à-dire un solvant ou un mélange de solvants et au moins un cosolvant, c'est-à-dire un cosolvant ou un mélange de cosolvants, et une fraction tensioactive, sous la forme d'une emulsion stable dans le temps, en conservant notamment sa souplesse, non ou faiblement nocive, peu inflammable et biodégradable. Avant d'exposer la présente invention, on définit ci-après quelques termes utilisés dans la description :A composition according to the invention comprises at least one solvent fraction comprising at least one solvent, that is to say a solvent or a mixture of solvents and at least one cosolvent, that is to say a cosolvent or a mixture cosolvents, and a surfactant fraction, in the form of an emulsion stable over time, in particular retaining its flexibility, non or slightly harmful, low flammability and biodegradable. Before explaining the present invention, some terms used in the description are defined below:
- une emulsion est constituée par la dispersion d'une phase dite interne dans une phase dite externe continue ;- An emulsion is formed by the dispersion of a so-called internal phase in a so-called continuous external phase;
- une microémulsion est constituée par une phase interne sous forme de microgouttelettes de taille 10 à 100 fois inférieure aux gouttelettes d'une emulsion définie ci-dessus ; - la phase interne est selon l'invention la phase solvante active vis-à-vis d'au moins une résine, comprenant au moins un solvant actif, et éventuellement au moins un cosolvant ; la phase externe est la phase continue de 1'emulsion, aqueuse ou non aqueuse, pouvant comprendre au moins un cosolvant ;- A microemulsion consists of an internal phase in the form of microdroplets of size 10 to 100 times smaller than the droplets of an emulsion defined above; - The internal phase according to the invention is the active solvent phase with respect to at least one resin, comprising at least one active solvent, and optionally at least one co-solvent; the external phase is the continuous phase of the emulsion, aqueous or non-aqueous, which may comprise at least one cosolvent;
- un cosolvant est un solvant ayant du non une activité solvant vis-à-vis d'au moins une résine, permettant de régler le pouvoir solvant spécifique de la fraction solvante le contenant; ce cosolvant peut lui même être soluble ou non dans la phase externe;- A cosolvent is a solvent having non-solvent activity with respect to at least one resin, making it possible to adjust the specific solvent power of the solvent fraction containing it; this cosolvent may itself be soluble or not in the external phase;
- par composition peu inflammable, on entend une composition dont le point éclair en coupe ouverte est supérieur à 50°C, et préférentiellement dont le point éclair est supérieur ou égal à 100°C.- A composition with low flammability is understood to mean a composition whose flash point in open section is greater than 50 ° C., and preferably whose flash point is greater than or equal to 100 ° C.
Selon la présente invention, on a découvert qu'une composition nettoyante, peu agressive, tant vis-à-vis de l'utilisateur que de l'environnement, facilement éliminable, stable et pratiquement non volatile, pouvait être obtenue, d'une part en réglant avec un cosolvant le pouvoir solvant de la fraction solvante, et d'autre part en utilisant conjointement avec la fraction solvante ainsi déterminée des agents tensioactifs spécifiques.According to the present invention, it has been discovered that a cleaning composition, not very aggressive, both vis-à-vis the user or the environment, easily removable, stable and practically non-volatile, could be obtained, on the one hand by adjusting with a cosolvent the solvent power of the solvent fraction, and on the other hand by using jointly with the solvent fraction thus determined specific surfactants.
Selon l'invention, en combinaison, d'une part, la fraction solvante est définie dans l'espace de Hansen par son paramètre partiel de polarité δp et son paramètre partiel de liaison hydrogène δh, à l'intérieur d'un parallélépipède dont la projection dans le plan δp, δh est une surface rectangulaire ayant une longueur sur l'axe δh de 16 (cal/cm3)1/2, soit 32,64 (J/cm3)1/2 à partir du point d'origine 0, et une largeur sur l'axe δp de 12 (cal/cm3)1/2, soit 24,48 (J/cm3)1/2 à partir du point d'origine 0, la valeur du paramètre partiel de dispersion δd n'étant pas limitative, et d'autre part, ladite fraction tensioactive comprend au moins un agent tensioactif non ionique principal choisi parmi les alcools, acides et esters gras éthoxylés ou non éthoxylés, dont la longue chaîne carbonée linéaire, saturée, hydrophobe possède au moins 18 atomes de carbone, et notamment 18 atomes de carbone. La théorie de Hansen et le calcul des paramètres δd, δp, δh ont fait l'objet de plusieurs publications telles que CM. HANSEN, J.P.T. (1967) 39, 104', dont le contenu est incorporé à la présente description si besoin est. Bien que, comme précité, la valeur δd ne soit pas limitative, elle est avantageusement comprise entre 7 et 10 (cal/cm3)1/2, soit entre 14,28 et 20,4 (J/cm3)1/2.According to the invention, in combination, on the one hand, the solvent fraction is defined in Hansen space by its partial parameter of polarity δp and its parameter partial connecting .DELTA.h hydrogen, inside of a parallelepiped whose projection in the plane Ap, .DELTA.h is a rectangular area having a length on the .DELTA.h axis 16 (cal / cm 3) 1/2, or 32, 64 (J / cm 3) 1/2 from the point of origin 0, and a width on the axis Ap of 12 (cal / cm 3) 1/2, or 24.48 (J / cm 3) 1 / 2 from the point of origin 0, the value of the partial dispersion parameter δd not being limiting, and on the other hand, said surfactant fraction comprises at least one main nonionic surfactant chosen from alcohols, acids and ethoxylated or non-ethoxylated fatty esters, the long linear, saturated, hydrophobic carbon chain of which has at least 18 carbon atoms, and in particular 18 carbon atoms. Hansen's theory and the calculation of the parameters δd, δp, δh have been the subject of several publications such as CM. HANSEN, JPT (1967) 39, 104 ' , the content of which is incorporated into the present description if necessary. Although, as mentioned above, the value Dd is not limitative, it is advantageously between 7 and 10 (cal / cm 3) 1/2, or between 14.28 and 20.4 (J / cm 3) 1/2 .
Selon l'invention, on entend par agent tensioactif principal, un tensioactif essentiel dans les compositions décrites et dont la proportion pondérale n'est pas nécessairement majoritaire dans ces compositions.According to the invention, the term “main surfactant” is intended to mean an essential surfactant in the compositions described and the proportion by weight of which is not necessarily the majority in these compositions.
Préférentiellement ledit tensioactif non ionique principal est lui-même défini dans l'espace de Hansen par son paramètre partiel de polarité δp et son paramètre partiel de liaison hydrogène δh, à l'intérieur du même parallélépipède que celui déterminé ci-dessus pour la fraction solvante.Preferably, said main nonionic surfactant is itself defined in the Hansen space by its partial parameter of polarity δp and its partial hydrogen bonding parameter δh, inside the same parallelepiped as that determined above for the solvent fraction. .
Selon une variante préférentielle de l'invention, le paramètre partiel de liaison hydrogène δh dudit agent tensioactif non ionique principal est supérieur à 3 (cal/cm3) ,2, soit 6,12 (J/cm3)72, ou mieux encore il est compris entre 3 (cal/cm3)1/2, soit 6,12 (J/cm3)1/2, et 8 (cal/cm3)1/2, soit 16,32 (J/cm3)l2, et son paramètre partiel de polarité δp est inférieur à 3 (cal/cm3)1/2, soit 6,12 (J/cm3)'/2. Ledit agent tensioactif non ionique principal est avantageusement présent dans la composition en une concentration pondérale comprise entre 1 et 15% du poids total de la composition.According to a preferred variant of the invention, the partial hydrogen bonding parameter δh of said main nonionic surfactant is greater than 3 (cal / cm 3 ) , 2 , or 6.12 (J / cm 3 ) 72 , or better still he is between 3 (cal / cm 3 ) 1/2 , or 6.12 (J / cm 3 ) 1/2 , and 8 (cal / cm 3 ) 1/2 , or 16.32 (J / cm 3 ) l2 , and its partial polarity parameter δp is less than 3 (cal / cm 3 ) 1/2 , or 6.12 (J / cm 3 ) ' / 2 . Said main nonionic surfactant is advantageously present in the composition in a weight concentration of between 1 and 15% of the total weight of the composition.
De manière préférentielle, cet agent tensioactif non ionique principal est choisi parmi le mono- et le distéarate de glycérol, le mono- et le distéarate de 1'éthylène-glycol, le mono- et le distéarate du diéthylène-glycol et le mono- et le distéarate du propylène-glycol, et l'alcool stéarylique éthoxylé avec un indice d'éthoxylation compris entre 2 et 21, et tout mélange de ceux-ci.Preferably, this main nonionic surfactant is chosen from glycerol mono- and distearate, ethylene glycol mono- and distearate, diethylene glycol mono- and distearate and mono- and propylene glycol distearate, and ethoxylated stearyl alcohol with an ethoxylation index of between 2 and 21, and any mixture thereof.
Avantageusement, la fraction externe' est elle aussi définie dans l'espace de Hansen par son paramètre partiel de polarité δp et son paramètre partiel de liaison hydrogène δh, à l'intérieur du même parallélépipède que celui déterminé pour la fraction solvante, c'est-à-dire un parallélépipède dont la projection dans le plan δp, δh est une surface rectangulaire ayant une longueur sur l'axe δh de 16 (cal/cm3)l2, soit 32,64 (J/cm3) l/2, à partir du point d'origine 0, et une largeur sur l'axe δp de 12 (cal/cm3)1/2, soit 24,48 (J/cm3)/2, à partir du point d'origine 0.Advantageously, the external fraction 'is also defined in Hansen space by its partial polarity parameter δp and its partial hydrogen bonding parameter δh, inside the same parallelepiped as that determined for the solvent fraction, that is i.e. a parallelepiped whose projection in the plane δp, δh is a rectangular surface having a length on the axis δh of 16 (cal / cm 3 ) l2 , or 32.64 (J / cm 3 ) l / 2 , from the point of origin 0, and a width on the axis δp of 12 (cal / cm 3 ) 1/2 , or 24.48 (J / cm 3 ) / 2 , from the point of origin 0.
De manière encore plus avantageuse, les paramètres partiels δp et δh de solubilité de la phase externe ont des valeurs comprises entre 0 et 10 (cal/cm3)72, soit 20,4 (J/cm3)l2, pour son paramètre partiel de polarité δp, et entre 3,5 (cal/cm3),2, soit 7,14 (J/cm3),/2, et 16 (cal/cm3)12, soit 32,64 (J/cm3)l/2, pour son paramètre partiel de liaison hydrogène δh, les valeurs de son paramètre partiel de dispersion δd étant de préférence choisi entre 7 (cal/cm3) Vl , soit 14,28 (J/cm3)'/2, et 10 (cal/cm3)'72, soit 20,4 (J/cm3),/2. Les compositions de 1 ' invention permettent d'exploiter au maximum les propriétés de la fraction solvante, tout en pouvant engager des concentrations faibles de cette dernière. En fonction de la formulation des différents ingrédients de la composition, il est possible d'obtenir des compositions possédant une activité polyvalente, c'est-à-dire susceptibles d'agir sur différents revêtements et salissures, ou bien des compositions très sélectives agissant spécifiquement sur tels revêtements ou salissures.Even more advantageously, the partial parameters δp and δh of solubility of the external phase have values between 0 and 10 (cal / cm 3 ) 72 , or 20.4 (J / cm 3 ) l2 , for its partial parameter polarity δp, and between 3.5 (cal / cm 3 ) , 2 , or 7.14 (J / cm 3 ) , / 2 , and 16 (cal / cm 3 ) 12 , or 32.64 (J / cm 3 ) l / 2 , for its partial hydrogen bonding parameter δh, the values of its partial dispersion parameter δd being preferably chosen between 7 (cal / cm 3 ) Vl , or 14.28 (J / cm 3 ) ' / 2 , and 10 (cal / cm 3 ) '72 , i.e. 20.4 (J / cm 3 ) , / 2 . The compositions of the invention make it possible to exploit the properties of the solvent fraction to the maximum, while being able to involve low concentrations of the latter. Depending on the formulation of the various ingredients of the composition, it is possible to obtain compositions having a versatile activity, that is to say capable of acting on different coatings and soiling, or else very selective compositions acting specifically on such coatings or soiling.
Selon l'invention, ledit cosolvant sera choisi en fonction des solubilités réciproques du solvant et du cosolvant, ainsi que de leurs solubilités respectives dans l'eau.According to the invention, said cosolvent will be chosen as a function of the reciprocal solubilities of the solvent and of the cosolvent, as well as of their respective solubilities in water.
En particulier, l'utilisation d'un cosolvant soluble dans l'eau avec un solvant insoluble dans l'eau et dans ledit cosolvant, permettra d'engager une concentration minimale dudit solvant dans la composition. Préférentiellement le solvant est choisi parmi les dialkylesters, tels que les mélanges d'adipate, de glutarate et de succinate du type RPDE® (commercialisé par la Société Rhône-Poulenc) et DBE® (commercialisé par la Société Dupont de Nemours) , mais aussi le dibutylphtalate, parmi les monoalkylesters tels que le lactate d'éthyle, le lactate de butyle et autres esters de l'acide lactique, le carbonate de propylène, le carbonate d'éthylène, parmi les esters d'éthers de 1 'éthylène-glycol, les esters d'éthers du propylène-glycol, tels que l'acétate de propylène- glycol-méthyléther, le diacetate de propylène-glycol, les méthoxy-esters et les éthoxy-ester comme l'éthoxy-3- propionate d'éthyle (en abrégé EEP) , parmi les éthers de 1 'éthylène-glycol et les éthers du propylène glycol, peu solubles ou insolubles dans l'eau, tels que les éthers mono-n-butyliques du propylène glycol, du dipropylène glycol et du tripropylène glycol, 1 'éther mono-t-butylique du propylène glycol (en abrégé PTB) , et 1 'éther monophénylique du propylène glycol, parmi les cétones telles que la méthylphénylcétone, la N-méthyl-pyrrolidone, la méthylisobutylcétone et la cyclohexanone, parmi les acides organiques tels que les mono- et di-acides carboxyliques et les acides polyfonctionnels tels que l'acide oxalique, l'acide citrique, l'acide lactique, et parmi les bases organiques telles que les alkylamines, ou les mélanges de ceux-ci. Le cosolvant est avantageusement choisi parmi les dérivés du glycol comprenant le mono-, le di- et le tri- et autres polyéthylènes et polypropylènes glycol, et l'hexylène glycol, parmi le glycérol, le sorbitol, le dextrose et le saccharose, parmi les éthers de l'éthylène- glycol et les éthers du propylène-glycol, solubles ou moyennement solubles dans l'eau, tels que le propylène glycol méthyl éther, le dipropylène glycol méthyl éther et le tripropylène glycol méthyl éther, parmi les alcools aliphatiques et aromatiques tels que l'alcool benzylique, parmi l'acétone, la N-méthyl-2-pyrrolidone, la 7- butyrolactone, ainsi que l'eau, ou tout mélange de ceux- ci.In particular, the use of a water-soluble cosolvent with a solvent insoluble in water and in said cosolvent, will make it possible to initiate a minimum concentration of said solvent in the composition. Preferably, the solvent is chosen from dialkylesters, such as mixtures of adipate, glutarate and succinate of the RPDE® type (marketed by the company Rhône-Poulenc) and DBE® (marketed by the company Dupont de Nemours), but also dibutylphthalate, among monoalkylesters such as ethyl lactate, butyl lactate and other lactic acid esters, propylene carbonate, ethylene carbonate, among ethylene glycol ether esters , esters of propylene glycol ethers, such as propylene glycol methyl acetate, propylene glycol diacetate, methoxy esters and ethoxy esters such as ethyl 3-propionate (abbreviated as EEP), among ethers of ethylene glycol and ethers of propylene glycol, poorly soluble or insoluble in water, such as mono-n-butyl ethers of propylene glycol, dipropylene glycol and tripropylene glycol, 1 'mono-t-butyl ether ique propylene glycol (abbreviated as PTB), and the monophenyl ether of propylene glycol, among ketones such as methylphenylketone, N-methyl-pyrrolidone, methylisobutylketone and cyclohexanone, among organic acids such as mono- and di -carboxylic acids and polyfunctional acids such as oxalic acid, citric acid, lactic acid, and among organic bases such as alkylamines, or mixtures thereof. The cosolvent is advantageously chosen from glycol derivatives comprising mono-, di- and tri- and other polyethylenes and polypropylenes glycol, and hexylene glycol, from glycerol, sorbitol, dextrose and sucrose, from ethylene glycol ethers and propylene glycol ethers, soluble or moderately soluble in water, such as propylene glycol methyl ether, dipropylene glycol methyl ether and tripropylene glycol methyl ether, among aliphatic and aromatic alcohols such as benzyl alcohol, among acetone, N-methyl-2-pyrrolidone, 7-butyrolactone, as well as water, or any mixture of these.
Avantageusement, la fraction solvante sera constituée par un diméthylester ou un mélange de diméthyleεters, comme solvant, et le monopropylene glycol, le glycérol, l'hexylène glycol ou un polypropylène glycol de poids moléculaire moyen supérieur ou égal à 400, comme cosolvant.Advantageously, the solvent fraction will consist of a dimethylester or a mixture of dimethyl esters, as solvent, and the monopropylene glycol, glycerol, hexylene glycol or a polypropylene glycol of average molecular weight greater than or equal to 400, as cosolvent.
Selon l'invention, la concentration pondérale de la fraction solvante, comprenant au moins ledit solvant et un cosolvant, est comprise entre 1 et 90% du poids total de la composition.According to the invention, the weight concentration of the solvent fraction, comprising at least said solvent and a cosolvent, is between 1 and 90% of the total weight of the composition.
La fraction tensioactive des compositions de l'invention comprend en outre au moins un autre agent tensioactif, différent de l'agent tensioactif principal, 8The surfactant fraction of the compositions of the invention also comprises at least one other surfactant, different from the main surfactant, 8
choisi parmi les agents tensioactifs non-ioniques, les agents tensioactifs anioniques, a photères et cationiques.chosen from nonionic surfactants, anionic, photeric and cationic surfactants.
L'autre agent tensioactif non ionique, différent de l'agent tensioactif principal, sera de préférence choisi parmi les acides gras éthoxylés, les alcools gras éthoxylés, les nonylphénols éthoxylés, les alkylpolyglucosides, les amides gras éthoxylés ou non, les esters de sorbitanne éthoxylés ou non, les alcanolamides.The other nonionic surfactant, different from the main surfactant, will preferably be chosen from ethoxylated fatty acids, ethoxylated fatty alcohols, ethoxylated nonylphenols, alkylpolyglucosides, ethoxylated or non-ethoxylated fatty amides, sorbitan esters or not, the alkanolamides.
L'autre agent tensioactif anionique sera de préférence choisi parmi les alkylsulfates, les alkyléthersulfates, les alkylsulfosuccinates, les esters phosphoriques d'alcool gras éthoxylé.The other anionic surfactant will preferably be chosen from alkyl sulfates, alkyl ether sulfates, alkyl sulfosuccinates, phosphoric esters of ethoxylated fatty alcohol.
L'autre agent tensioactif amphotère sera préférentiellement choisi parmi les dérivés des alkylbétaïnes.The other amphoteric surfactant will preferably be chosen from alkylbetaine derivatives.
Quand elle est destinée à incorporer une crème lavante pour les mains, une composition de l'invention comprend à titre d'agent tensioactif différent de l'agent tensioactif principal, un mélange d'agents tensioactifs possédant une chaîne carbonée en C12~ci8' c'est-à-dire C12, C 14' C 16/ i8/ avec une proportion pondérale en agents tensioactifs en C^g-Ciβ, au moins équivalente à celle en agents tensioactifs en C\2~c \ -When it is intended to incorporate a hand washing cream, a composition of the invention comprises, as surfactant different from the main surfactant, a mixture of surfactants having a carbon chain of C 12 ~ c i 8 ', that is to say C 12 , C 14 ' C 16 / i 8 / with a weight proportion of surfactants in C ^ g-Ciβ, at least equivalent to that in surfactants in C \ 2 ~ c \ -
Pour cette application, une composition de l'invention comprendra avantageusement :For this application, a composition of the invention will advantageously include:
- 1 à 30% en poids d'esters dibasiques, à titre de solvant,- 1 to 30% by weight of dibasic esters, as solvent,
- 1 à 30% en poids de monopropylene glycol ou glycérol, à titre de cosolvant, - 1 à 15% en poids de mono- ou distéarate de glycérol, à titre d'agent tensioactif principal,- 1 to 30% by weight of monopropylene glycol or glycerol, as cosolvent, - 1 to 15% by weight of glycerol mono- or distearate, as main surfactant,
- 1 à 30% en poids d'agents tensioactifs, différents de l'agent tensioactif principal, choisis parmi les tensioactifs non ioniques, anioniques et/ou amphotères, - de l'eau. Une crème lavante de l'invention particulièrement avantageuse possède un pouvoir solvant complémentaire vis- à-vis des corps gras apporté par la fraction tensioactive.- 1 to 30% by weight of surfactants, different from the main surfactant, chosen from nonionic, anionic and / or amphoteric surfactants, - water. A particularly advantageous washing cream of the invention has a complementary solvent power with respect to fatty substances provided by the surfactant fraction.
Quand elle est destinée à incorporer une préparation décapante, une composition de l'invention comprend, à titre d'agent tensioactif différent de l'agent tensioactif principal, au moins un agent tensioactif choisi parmi ceux ayant une chaîne carbonée en C8-C12 et qui sont éthoxylés avec un indice d'éthoxylation compris entre 1 et 5, ou non éthoxylés.When it is intended to incorporate a stripping preparation, a composition of the invention comprises, as surfactant different from the main surfactant, at least one surfactant chosen from those having a carbon chain C8-C12 and which are ethoxylated with an ethoxylation index between 1 and 5, or not ethoxylated.
Pour cette application, une composition de 1' invention comprendra avantageusement :For this application, a composition of the invention will advantageously include:
- une fraction solvante dans une proportion de 1 à 90% en poids, - 1 à 15% en poids de mono- ou distéarate de glycérol,- a solvent fraction in a proportion of 1 to 90% by weight, - 1 to 15% by weight of glycerol mono- or distearate,
- 1 à 50% en poids d'agents tensioactifs différents de l'agent tensioactif principal- 1 to 50% by weight of surfactants different from the main surfactant
- 0 à 88 % en poids d'eau.- 0 to 88% by weight of water.
La concentration pondérale de l'agent tensioactif, ou des agents tensioactifs différents de l'agent tensioactif principal, est au plus égale à 50%.The weight concentration of the surfactant, or of surfactants other than the main surfactant, is at most equal to 50%.
Des additifs peuvent être ajoutés aux compositions de l'invention, en particulier des sels neutres, acides ou alcalins, organiques ou minéraux, ou bien des acides ou bases organiques ou minéraux. Ils peuvent être dissous ou non et se présenter »alors dans toute emulsion ou composition selon l'invention sous la forme d'une charge comme une poudre fine en suspension, qui favorise l'adsorption des pigments de la résine éliminée par la composition de l'invention. En outre, un nettoyage plus rapide et plus complet au moment du rinçage du support est aussi obtenu.Additives can be added to the compositions of the invention, in particular neutral, acid or alkaline, organic or mineral salts, or alternatively organic or mineral acids or bases. They may or may not be dissolved and may then be present "in any emulsion or composition according to the invention in the form of a filler such as a fine powder in suspension, which promotes the adsorption of the pigments of the resin eliminated by the composition of the 'invention. In addition, faster and more complete cleaning when rinsing the support is also obtained.
Les caractéristiques de l'invention sont à présent illustrées par le dessin annexé et par les exemples suivants, d'où ressortiront d'autres avantages et applications des présentes compositions. 10The characteristics of the invention are now illustrated by the appended drawing and by the following examples, from which other advantages and applications of the present compositions will emerge. 10
Dans le dessin,In the drawing,
- la figure 1 représente la projection dans le plan (δp,δh) des volumes de solubilité selon la théorie d'Hansen de deux résines Rx et Ry, ayant en commun un ensemble de points;- Figure 1 shows the projection in the plane (δp, δh) of the solubility volumes according to the Hansen theory of two resins Rx and Ry, having in common a set of points;
- la figure 2 représente la projection dans le plan (δp,δh) des points définis dans l'espace de Hansen des fractions solvantes Ll, L2, L3, L4 , N, D, Ml, MG1, MG2 , MG3, MG4, qui font l' objet des exemples 4, 5, et 6, et des points définis dans le même espace des solvants purs.- Figure 2 represents the projection in the plane (δp, δh) of the points defined in the Hansen space of the solvent fractions Ll, L2, L3, L4, N, D, Ml, MG1, MG2, MG3, MG4, which are the subject of examples 4, 5, and 6, and points defined in the same space of pure solvents.
Exemple 1:Example 1:
Mode de préparation des émulsionsMethod of preparing emulsions
Ces émulsions se préparent selon la méthode d'emulsion directe. Les constituants tensioactifs et l'eau, si celle-ci est prévue en tant que phase externe dans la composition, ou le composant constituant la phase externe de 1 'emulsion, sont chauffés à 70°C/80°C et mélangés parfaitement. Puis on ajoute sous agitation constante le ou les cosolvants puis le ou les solvants, ou les deux en même temps. L'agitation est maintenue constante jusqu'à refroidissement complet au cours duquel 1'emulsion se forme.These emulsions are prepared according to the direct emulsion method. The surface-active constituents and the water, if this is provided as an external phase in the composition, or the component constituting the external phase of the emulsion, are heated to 70 ° C / 80 ° C and mixed perfectly. Then the cosolvent (s) and then the solvent (s) or both are added with constant stirring. Stirring is kept constant until complete cooling during which the emulsion is formed.
Exemple 2 :Example 2:
Utilisation de la théorie d'Hansen pour préparer une composition nettoyante de l'invention à activité spécifiqueUse of Hansen's theory to prepare a cleaning composition of the invention with specific activity
Méthode générale :General method:
Pour préparer de telles compositions, il est nécessaire de connaître le ou les volumes de solubilité dans l'espace (δd, δp, δh) de la ou des résines à nettoyer. Ceci s'obtient expérimentalement en étudiant l'action sur chaque résine de différentes fractions solvantes (à % V variable) d'au moins deux solvants connus.To prepare such compositions, it is necessary to know the volume or volumes of solubility in space (δd, δp, δh) of the resin or resins to be cleaned. This is obtained experimentally by studying the action on each resin of different fractions solvents (with variable% V) of at least two known solvents.
Ces essais sont réalisés avec différents couples de solvants dont on connait ou dont on a calculé les paramètres de solubilité. Chaque fraction solvante est représentée par un point dans l'espace de Hansen.These tests are carried out with different pairs of solvents for which we know or for which the solubility parameters have been calculated. Each solvent fraction is represented by a point in Hansen space.
Les fractions suivantes sont classées en trois catégories : actives, peu actives (action limite) ou inactives. Les points représentatifs des fractions actives sont situés à l'intérieur du volume de solubilité de la résine étudiée. Les points représentatifs des fractions peu actives sont situés sur l'enveloppe de ce volume de solubilité. Les points représentatifs des fractions inactives sont situés à l'extérieur de ce même volume. Pour des raisons pratiques, et conformément à laThe following fractions are classified into three categories: active, not very active (limiting action) or inactive. The representative points of the active fractions are located inside the solubility volume of the resin studied. The representative points of the inactive fractions are located on the envelope of this volume of solubility. The representative points of the inactive fractions are located outside this same volume. For practical reasons, and in accordance with the
Fig 1, on représente ce volume de solubilité par sa projection sur le plan (δp, δh) , parallèlement à 'l'axe δd.Fig 1, we represent this volume of solubility by its projection on the plane (δp, δh), parallel to ' the axis δd.
Sur la figure 1, le point A représente une fraction solvante active sur les deux résines Rx et Ry. Le point C représente une fraction solvante active seulement sur la résine Rx. Les points D et B représentent deux fractions solvantes inactives sur Rx et Ry. Chaque point peut représenter soit un solvant pur, soit un mélange de plusieurs solvants. Si le point A représente un solvant pur A et le point B un cosolvant pur B, par mélange de A et B dans des rapports en volume convenables, on réalisera une fraction solvante C qui sera active sur la résine Rx et inactive sur la résine Ry.In FIG. 1, point A represents a solvent fraction active on the two resins Rx and Ry. Point C represents a solvent fraction active only on the resin Rx. Points D and B represent two inactive solvent fractions on Rx and Ry. Each point can represent either a pure solvent or a mixture of several solvents. If point A represents a pure solvent A and point B a pure cosolvent B, by mixing A and B in suitable volume ratios, a solvent fraction C will be produced which will be active on the resin Rx and inactive on the resin Ry .
Exemple 3:Example 3:
Préparation et utilisation d'une composition décapante selon l'inventionPreparation and use of a stripping composition according to the invention
La formulation de la composition I selon l'invention est la suivante, donnée en pourcentage en poids, la phase interne de l'emulsion consistant en la fraction solvante et la phase externe en de l'eau mélangée à la fraction tensioactive :The formulation of composition I according to the invention is as follows, given as a percentage weight, the internal phase of the emulsion consisting of the solvent fraction and the external phase of water mixed with the surfactant fraction:
*Praction solvante: Solvants; ester dibasique DBE® 25 phtalate de dibutyle DBP 25 acide formique 0,8 Cosolvant: tripropylène glycol 11* Solvent praction: Solvents; dibasic ester DBE® 25 dibutyl phthalate DBP 25 formic acid 0.8 Cosolvent: tripropylene glycol 11
*Fraction tensioactive:* Surfactant fraction:
Agent tensioactif principal: monostéarate de glycérol 10Main surfactant: glycerol monostearate 10
Autres agents tensioactifs: Alkylεulfate en C10-C16 6Other surfactants: C 10 -C 16 6 alkyl sulphate
(90% de matières actives)(90% active ingredients)
Alcool gras C10-C12 éthoxylé ( 50E) 3C 10 -C 12 fatty alcohol ethoxylated (50E) 3
*Eau 19 , 2* Water 19, 2
La composition I a été testée sur des plaques test de métal revêtu d'un primaire d'accrochage sur lequel ont été appliquées les peintures suivantes :Composition I was tested on metal test plates coated with a bonding primer on which the following paints were applied:
1) Peinture glycérophtalique brillante séchée à l'air correspondant au type de peinture utilisée dans l'industrie et le bâtiment, et autrefois dans 1 'automobile. 2) Peinture glycérophtalique brillante séchée au four 3 heures à 100°C (vieillissement accéléré) .1) Brilliant air-dried glycerophthalic paint corresponding to the type of paint used in industry and building, and formerly in the automobile. 2) Brilliant glycerophthalic paint dried in the oven for 3 hours at 100 ° C (accelerated aging).
3) Peinture de type cellulosique3) Cellulosic paint
4) Peinture polyuréthane à deux composants, brillant direct, séchée au four pendant une heure à 80°C (type de peinture automobile actuelle) . Le tableau 1 ci-dessous donne les résultats de ces essais et des temps de décapage nécessaires selon les résines à éliminer, l'épaisseur des films à retirer variant de 40 à 50 μm. TABLEAU 14) Two-component polyurethane paint, direct gloss, oven-dried for one hour at 80 ° C (current type of automotive paint). Table 1 below gives the results of these tests and the etching times required depending on the resins to be removed, the thickness of the films to be removed varying from 40 to 50 μm. TABLE 1
Type de peinture 1 2 3 4 temps minimum de 9 min 75 min 60 min 80 min décapage *Type of paint 1 2 3 4 minimum time of 9 min 75 min 60 min 80 min pickling *
* élimination de la résine et du primaire d'accrochage* elimination of resin and bonding primer
Les paramètres partiels de solubilité de la phase solvante de la composition I correspondent sur la Fig 1 à un point du type point A qui est situé à l'intérieur des volumes de solubilité des différentes résines décapées, et sur la Figure 2, au point D.The partial solubility parameters of the solvent phase of composition I correspond in FIG. 1 to a point of the type point A which is located inside the solubility volumes of the different pickled resins, and in FIG. 2, to point D .
Ces valeurs démontrent bien l'avantage de l'utilisation de telles compositions qui sont pratiquement sans odeur, non volatiles, peu inflammables et non nocives, en remplacement des décapants à base de chlorure de méthylène, très volatil, et très nocif et qui peuvent provoquer des effets irréversibles sur la santé des utilisateurs.These values clearly demonstrate the advantage of using such compositions which are practically odorless, non-volatile, not very flammable and not harmful, replacing strippers based on methylene chloride, which are very volatile and very harmful and which can cause irreversible effects on the health of users.
Des compositions comme la composition I sont certes plus lentes que les décapants à base de chlorure de méthylène, mais elles présentent l'avantage de décaper plus profondément en une seule opération, sans évaporation et sans sécher. La composition I après 48 heures à 35°C est toujours souple et parfaitement rinçable à l'eau.Compositions like composition I are certainly slower than strippers based on methylene chloride, but they have the advantage of stripping more deeply in a single operation, without evaporation and without drying. Composition I after 48 hours at 35 ° C is still flexible and perfectly rinsable with water.
Ces compositions ne craignent pas le gel et résistent parfaitement à des cycles de variation de températures entre -15°C et +40°C sans altération de 1'emulsion, celle-ci reprenant ses caractéristiques initiales par retour à la température ambiante. Exemple 4:These compositions are not afraid of freezing and are perfectly resistant to temperature variation cycles between -15 ° C. and + 40 ° C. without alteration of the emulsion, the latter resuming its initial characteristics by returning to room temperature. Example 4:
Détermination de la fraction solvante d'une composition de l'invention destinée au nettoyage d'une salissure constituée d'une résine Rx appliquée sur un support soit revêtu d'un revêtement superficiel Ry, soit constitué dans sa masse, par une résine Ry que l'on veut préserver et restaurer.Determination of the solvent fraction of a composition of the invention intended for cleaning a dirt consisting of an Rx resin applied to a support either coated with a Ry surface coating, or constituted in its bulk, by a Ry resin that we want to preserve and restore.
Ce cas est illustré sur la figure 2. Le tableau 2 suivant rapporte les résultats obtenus expérimentalement qui déterminent les limites (c'est-à-dire l'enveloppe) du volume de solubilité, pour quelques couples de solvants d'une résine Rx à nettoyer.This case is illustrated in FIG. 2. The following table 2 reports the results obtained experimentally which determine the limits (that is to say the envelope) of the volume of solubility, for a few pairs of solvents of a resin Rx at clean.
La résine Rx est une peinture cellulosique ayant la couleur noir mat. Rx resin is a cellulosic paint with a matt black color.
TABLEAU 2TABLE 2
Solvant Cosolvant Fraction solvanteSolvent Cosolvent Solvent fraction
Type concentra¬ concentra¬ δh, δp, δd* tion Type tion Type δh δp δd pondérale pondérale ester dibasique densité 1,092 19,9 8,2 16.7 δh 9,8 (4,8) 25 75 l (9,75) (4.02) (8,2) δp 4,7 (2,3) δd 16,9 (8,3) tripropylène glycol monopropylèneglycol densité 1,024 densité 1,032 1K.4 6,3 16,1 δh 15,9 (7,8) 66,7 δh 23,25 (11,4) 33,3 2 (9,0) (3.D (7,9) δp 4,9 (2,4) δp 9,4 (4,6) δd 15,9 (7,8) δd 16,7 (8,2)Type concentra¬ concentra¬ δh, δp, δd * tion Type tion Type δh δp δd weight by weight dibasic ester density 1.092 19.9 8.2 16.7 δh 9.8 (4.8) 25 75 l (9.75) (4.02 ) (8.2) δp 4.7 (2.3) δd 16.9 (8.3) tripropylene glycol monopropylene glycol density 1.024 density 1.032 1K.4 6.3 16.1 δh 15.9 (7.8) 66 , 7 δh 23.25 (11.4) 33.3 2 (9.0) (3.D (7.9) δp 4.9 (2.4) δp 9.4 (4.6) δd 15, 9 (7.8) δd 16.7 (8.2)
N-inéthylpyrrolidone densité 1,031 19,2 10,1 !7,0 δh 7,1 (3,5) 25 75 L3 (9,42) (4,95) (8.35) δp 12,24 (6,0) δd 17,9 (8,8) glycérol densité 1,260 18,2 12,1 17,6N-inethylpyrrolidone density 1.031 19.2 10.1! 7.0 δh 7.1 (3.5) 25 75 L3 (9.42) (4.95) (8.35) δp 12.24 (6.0) δd 17.9 (8.8) glycerol density 1,260 18.2 12.1 17.6
50 δh 29,2 (14,3) 50 L4 (8,9) (5,95) (8,65) δp 12,0 (5,9) δd 17,3 (8,5) δh, δp, δd sont exprimés en (J/cnrr)'2, et entre parenthèse en (cal/cm^)'2 50 δh 29.2 (14.3) 50 L4 (8.9) (5.95) (8.65) δp 12.0 (5.9) δd 17.3 (8.5) δh, δp, δd are expressed in (J / cnrr) ' 2 , and in parenthesis in (cal / cm ^)' 2
Les valeurs calculées de δd, δp, δh pour les quatre mélanges cités déterminent les quatre points limites représentant quatre fractions solvantes en limite d'action sur la résine Rx qui est une peinture cellulosique noir mat, à nettoyer. Ces quatre points déterminent une portion du volume de solubilité de la résine Rx.The calculated values of δd, δp, δh for the four mixtures mentioned determine the four limit points representing four solvent fractions at the limit of action on the resin Rx which is a matt black cellulose paint, to be cleaned. These four points determine a portion of the volume of solubility of the resin Rx.
La figure 2 représente la projection sur la plan δp, δh de ces points et de quelques solvants purs, la valeur de δd pour ces points étant entre parenthèses.FIG. 2 represents the projection on the plane δp, δh of these points and of some pure solvents, the value of δd for these points being in parentheses.
La portion de courbe reliant les points Ll, L2, L3 , L4 représente la projection sur le plan (δp, δh) de la portion du volume de solubilité de la résine Rx déterminée précédemment. Les points à droite de cette courbe représentent des fractions solvantes inactives sur la résine Rx. Les points à gauche de cette même courbe représentent les fractions solvantes actives.The portion of the curve connecting the points L1, L2, L3, L4 represents the projection onto the plane (δp, δh) of the portion of the volume of solubility of the resin Rx determined previously. The points to the right of this curve represent inactive solvent fractions on the Rx resin. The points to the left of this same curve represent the active solvent fractions.
Exemple 5:Example 5:
Application d'une composition de l'invention au nettoyage spécifique d'une peinture cellulosique noire à enlever sur divers types de peinture à préserverApplication of a composition of the invention to the specific cleaning of a black cellulosic paint to be removed on various types of paint to be preserved
L'exemple suivant est réalisé sur quatre plaques test en métal revêtu d'un primaire d'accrochage sur lequel on a appliqué les peintures suivantes :The following example is carried out on four metal test plates coated with a bonding primer on which the following paints have been applied:
1) Peinture glycérophtalique brillante séchée à température ambiante, très récente (appliquée 7 jours avant le test de nettoyage) . Ce film demeure très fragile à une attaque de solvant.1) Brilliant glycerophthalic paint dried at room temperature, very recent (applied 7 days before the cleaning test). This film remains very fragile to a solvent attack.
2) Peinture glycérophtalique brillante séchée au four pendant 3 heures à 100°C (vieillissement accéléré) .2) Brilliant glycerophthalic paint dried in the oven for 3 hours at 100 ° C (accelerated aging).
3) Peinture alkyde "pochée", "satinée" d'un type couramment utilisé en peinture pour le bâtiment pour l'extérieur et l'intérieur (appliquée depuis 15 jours) . 4) Peinture de façades, blanche, à la Pliolite® (commercialisé par la Société Goodyear) imperméable et microporeuse (appliquée depuis 15 jours) .3) Alkyd paint "poached", "satin" of a type commonly used in paint for the building for exterior and interior (applied for 15 days). 4) White, Pliolite® facade paint (marketed by the Goodyear Company) waterproof and microporous (applied for 15 days).
Sur ces quatre tests, on applique par pulvérisation une peinture cellulosiqueOn these four tests, a cellulosic paint is applied by spraying
La formulation de la composition II utilisée est la suivante, donnée en pourcentage en poids :The formulation of composition II used is the following, given as a percentage by weight:
*Fraction solvante: ester dibasique DBE® (solvant) 25 monopropylene glycol (cosolvant) 20* Solvent fraction: DBE® dibasic ester (solvent) 25 monopropylene glycol (cosolvent) 20
*Fraction tensioactive:* Surfactant fraction:
Agent tensioactif principal: monostéarate de glycérol 10Main surfactant: glycerol monostearate 10
Autres agents tensioactifs: acide oléique éthoxylé (60E) 23 alkylsulfates en C10-C16 2Other surfactants: ethoxylated oleic acid (60E) 23 C 10 -C 16 alkyl sulfates 2
(90% de matière active)(90% active ingredient)
*Eau 19,2* Water 19.2
Le point N sur la Figure 2 représente la position dans l'espace de Hansen et dans le plan (δp, δh) de la fraction solvante de la composition II.Point N in Figure 2 represents the position in Hansen space and in the plane (δp, δh) of the solvent fraction of composition II.
La composition II est appliquée comme suit:Composition II is applied as follows:
- une première application est effectuée avec un pinceau, ou brosse douce ou chiffon doux pendant 2 mn; l'action mécanique accélère la dissolution et la mise en emulsion des pigments de la peinture cellulosique- a first application is made with a brush, or soft brush or soft cloth for 2 minutes; mechanical action accelerates the dissolution and emulsification of pigments in cellulosic paint
- rinçage à l'eau- rinsing with water
- une deuxième applicaion est effectuée sur surface sèche pour terminer le nettoyage, avec une action mécanique comme précédemment pendant 1 mn - rinçage à l'eau. Le temps total maximum pour chaque essai est inférieur ou égal à 5 mn pour un nettoyage complet de la peinture cellulosique. Les quatre films de peinture à restaurer et à préserver sont parfaitement intacts. La composition II possède une fraction solvante émulsionnée : a) suffisamment solvante pour dissoudre la peinture cellulosique constituée d'une résine et de pigments, lesquels sont émulsionnés et maintenus dans 1 'emulsion de la composition, par la phase tensioactive de cette dernière, et ces salissures deviennent alors facilement rinçables à l'eau b) suffisamment douce pour ne pas altérer le film de peinture à restaurer pendant le temps nécessaire au nettoyage.- a second application is made on a dry surface to complete the cleaning, with a mechanical action as before for 1 min - rinsing with water. The maximum total time for each test is less than or equal to 5 min for a complete cleaning of the cellulosic paint. The four paint films to restore and preserve are perfectly intact. Composition II has an emulsified solvent fraction: a) sufficiently solvent to dissolve the cellulose paint consisting of a resin and pigments, which are emulsified and maintained in the emulsion of the composition, by the surfactant phase of the latter, and these soiling becomes easily rinsable with water b) soft enough not to alter the paint film to be restored for the time necessary for cleaning.
L'exemple cité montre bien la grande versatilité de telles compositions et les avantages qu'elles procurent aux utilisateurs. La composition II est pratiquement sans odeur, non volatile, non inflammable, non nocive, totalement biodégradable, et très efficace avec une concentration faible de solvant actif (DBE® 25% poids/poids) .The example cited clearly shows the great versatility of such compositions and the advantages that they provide to users. Composition II is practically odorless, non-volatile, non-flammable, non-harmful, completely biodegradable, and very effective with a low concentration of active solvent (DBE® 25% w / w).
Les variantes citées ci-dessous dans le tableau 3 avec différents tensioactifs principaux donnent les mêmes résultats de nettoyage (la viscosité finale étant seule modifiée) . The variants cited below in Table 3 with different main surfactants give the same cleaning results (the final viscosity only being modified).
TABLEAU 3TABLE 3
Figure imgf000021_0001
Figure imgf000021_0001
Exemple 6:Example 6:
Préparation d'une composition de l'invention pour le nettoyage des mainsPreparation of a composition of the invention for cleaning the hands
a) cas d'une composition dont la fraction solvante comprend un solvant soluble dans le cosolvant et un cosolvant soluble dans l'eau, ce qui signifie que la phase interne de l'emulsion est constituée du solvant et du cosolvant et la phase externe est aqueuse et peut éventuellement comprendre un peu de la fraction solvante.a) case of a composition in which the solvent fraction comprises a solvent soluble in the cosolvent and a cosolvent soluble in water, which means that the internal phase of the emulsion consists of the solvent and the co-solvent and the external phase is aqueous and may optionally comprise a little of the solvent fraction.
La formulation de la composition III utilisée est la suivante, donnée en pourcentage en poids :The formulation of composition III used is the following, given as a percentage by weight:
*Fraction solvante: esters dibasiques (solvant) 15 monopropylene glycol (cosolvant) 10* Solvent fraction: dibasic esters (solvent) 15 monopropylene glycol (cosolvent) 10
*Fraction tensioactive:* Surfactant fraction:
Agent tensioactif principal: monostéarate de glycérol 8Main surfactant: glycerol monostearate 8
Autres agents tensioactifs: alkylsulfate en C12 -Ci8 10 monopalmitate de sorbitan éthoxylé (200E) 2Other surfactants: C 12 -C i alkyl sulfate 8 10 ethoxylated sorbitan monopalmitate (200E) 2
*Eau 55* Water 55
Le point Ml représenté à la Fig 2 correspond à une fraction de solvant à teneur réduite en solvant actif. Mais il permet d'enlever parfaitement les salissures très incrustantes telles que peintures, mastics, encres, etc..The point M1 represented in FIG. 2 corresponds to a fraction of solvent with a reduced content of active solvent. But it makes it possible to remove very encrusting dirt perfectly such as paints, mastics, inks, etc.
b) cas d'une composition dont la fraction solvante comprend un solvant insoluble dans le cosolvant et un cosolvant soluble dans l'eau, ce qui signifie que la phase interne de l'emulsion n'est constituée que du solvant et la phase externe est aqueuse et comprend le cosolvant. Quatre compositions MG1 à MG4 ont été préparées, leurs formulations sont présentées dans le tableau 4 ci- après.b) case of a composition in which the solvent fraction comprises a solvent insoluble in the co-solvent and a water-soluble co-solvent, which means that the internal phase of the emulsion consists only of the solvent and the external phase is aqueous and includes the co-solvent. Four compositions MG1 to MG4 were prepared, their formulations are presented in Table 4 below.
TABLEAU 4TABLE 4
COMPOSITION MG1 MG2 MG3 MG4COMPOSITION MG1 MG2 MG3 MG4
Fraction solvante DBE® 17,3 15 11 7,7 Glycérol 7,7 10 14 17,3Solvent fraction DBE® 17.3 15 11 7.7 Glycerol 7.7 10 14 17.3
Fraction tensioactiveSurfactant fraction
Mono-distéarate de Glycérol 10 10 10 10 Alkyl sulfate C12 _C18 10 10 10 10 Alkyl sulfate C^g-C^ 2 2 2 2Glycerol mono-distearate 10 10 10 10 Alkyl sulfate C 12 _C 18 10 10 10 10 Alkyl sulfate C ^ gC ^ 2 2 2 2
Eau 53 53 53 . 53Water 53 53 53. 53
100 100 100 100100 100 100 100
La théorie de Hansen permet de calculer la position théorique du pouvoir solvant d'un mélange, même s'il est constitué d'au moins deux constituants insolubles; dans ce cas particulier, on parlera de points virtuels, obtenus par projection dans le plan (δp, δh) .Hansen's theory makes it possible to calculate the theoretical position of the solvent power of a mixture, even if it consists of at least two insoluble constituents; in this particular case, we will speak of virtual points, obtained by projection in the plane (δp, δh).
Ainsi, les quatre points MG1, MG2, MG3, MG4 sont des points virtuels. Les compositions correspondantes MG3 et MG4 ne devraient pas être actives sur des salissures, or ces quatre compositions sont actives sur toutes les salissures de peinture et en particulier sur la peinture cellulosique noir mat. A l'équilibre, la phase interne de 1'emulsion ne contient que du DBE® émulsionné.Thus, the four points MG1, MG2, MG3, MG4 are virtual points. The corresponding compositions MG3 and MG4 should not be active on dirt, but these four compositions are active on all paint soils and in particular on matt black cellulose paint. At equilibrium, the internal phase of the emulsion contains only emulsified DBE®.
Ce cas permet d'engager des teneurs en solvant actif encore plus réduites que dans le cas précédent (la différence entre les quatre compositions réside uniquement dans la vitesse de nettoyage qui diminue de MG1 à MG4). This case makes it possible to engage contents of active solvent even lower than in the previous case (the difference between the four compositions lies only in the cleaning speed which decreases from MG1 to MG4).

Claims

REVENDICATIONS
1. Composition nettoyante ou décapante, sous la forme d'une emulsion ou microémulsion stable constituée par une phase interne, comprenant au moins une fraction solvante non ou peu nocive, peu inflammable et biodégradable, comportant au moins un solvant possédant un pouvoir solvant vis-à-vis d'au moins une résine, et une phase externe comportant une fraction tensioactive comprenant au moins un agent tensioactif non ionique principal, caractérisée en ce que en combinaison, d'une part ladite fraction solvante comprend en outre au moins un cosolvant, lesdits solvant et cosolvant étant choisis de manière que la fraction solvante est définie dans l'espace de Hansen par le paramètre partiel de polarité δp et le paramètre partiel de liaison hydrogène δh, à l'intérieur d'un parallélépipède dont la projection dans le plan δp, δh est une surface rectangulaire ayant une longueur sur l'axe δh de 16 (cal/cm3)/- , soit 32,64 (J/cm3)'2, à partir du point d'origine 0, et une largeur sur l'axe δp de 12 (cal/cm3)12, soit 24,48 (J/cm3),2, à partir du point d'origine 0, et d'autre part ledit agent tensioactif non ionique principal est choisi parmi les alcools, acides et esters gras éthoxylés ou non éthoxylés dont la longue chaîne carbonée linéaire, saturée, hydrophobe possède au moins 18 atomes de carbone, et notamment 18 atomes de carbone, ladite composition ne contenant pas ou presque pas d'épaississant.1. Cleaning or stripping composition, in the form of a stable emulsion or microemulsion constituted by an internal phase, comprising at least one solvent fraction which is not or not very harmful, not very flammable and biodegradable, comprising at least one solvent having a solvent power vis- with respect to at least one resin, and an external phase comprising a surfactant fraction comprising at least one main nonionic surfactant, characterized in that, in combination, on the one hand said solvent fraction further comprises at least one cosolvent, said solvent and co-solvent being chosen so that the solvent fraction is defined in Hansen space by the partial parameter of polarity δp and the partial hydrogen bonding parameter δh, inside a parallelepiped whose projection in the plane δp, δh is a rectangular surface having a length on the axis δh of 16 (cal / cm 3 ) / -, or 32.64 (J / cm 3 ) ' 2 , from the point of origin 0, and a width on the axis δp of 12 (cal / cm 3 ) 12 , ie 24.48 (J / cm 3 ) , 2 , from the point of origin 0, and on the other hand said nonionic surfactant main is chosen from ethoxylated or non-ethoxylated fatty alcohols, acids and esters whose long linear, saturated, hydrophobic carbon chain has at least 18 carbon atoms, and in particular 18 carbon atoms, said composition containing little or no thickening.
2. Composition selon la revendication 1, caractérisée en ce que ledit agent tensioactif non ionique principal est défini dans l'espace de Hansen par le paramètre partiel de polarité δp et le paramètre partiel de liaison hydrogène δh, à l'intérieur d'un parallélépipède dont la projection dans le plan δp, δh est une surface rectangulaire ayant une longueur sur l'axe δh de 16 (cal/cm3) ,2, soit 32,64 (J/cm3)'2, à partir du point d'origine 0, et une largeur sur l'axe δp de 12 (cal/cm3) V7i2, soit 24,48 (J/cm3),2, à partir du point d'origine 0.2. Composition according to claim 1, characterized in that said main nonionic surfactant is defined in the Hansen space by the partial parameter of polarity δp and the partial parameter of hydrogen bonding δh, inside a parallelepiped whose projection in the plane δp, δh is a rectangular surface having a length on the axis δh of 16 (cal / cm 3 ) , 2 , i.e. 32.64 (J / cm 3 ) ' 2 , from the point of origin 0, and a width on the axis δp of 12 (cal / cm 3 ) V 7 i 2 , i.e. 24.48 (J / cm 3 ) , 2 , from the point of origin 0.
3. Composition selon la revendication 2, caractérisée en ce que le paramètre partiel de liaison hydrogène δh dudit agent tensioactif non ionique principal est compris entre 3 (cal/cm3)l2, soit 6,12 (J/cm3)l2, et 8 (cal/cm3) l/2, soit 16,32 (J/cm3)12, et son paramètre partiel de polarité δp est inférieur à 3 (cal/cm3) l2, soit 6,12 (J/cm3)'2. 3. Composition according to claim 2, characterized in that the partial hydrogen bonding parameter δh of said main nonionic surfactant is between 3 (cal / cm 3 ) l2 , or 6.12 (J / cm 3 ) l2 , and 8 (cal / cm 3 ) l / 2 , or 16.32 (J / cm 3 ) 12 , and its partial polarity parameter δp is less than 3 (cal / cm 3 ) l2 , or 6.12 (J / cm 3 ) ' 2 .
4. Composition selon l'une quelconque des revendications 1 à 3, caractérisée en ce que ledit agent tensioactif non ionique principal est choisi parmi le mono- et le distéarate de glycérol, le mono- et le distéarate de l'éthylène-glycol, le mono- et le distéarate du diéthylène-glycol et le mono- et le distéarate du propylène-glycol, et l'alcool stéarylique éthoxylé avec un indice d'éthoxylation compris entre 2 et 21, ' et tout mélange de ceux-ci.4. Composition according to any one of claims 1 to 3, characterized in that said main nonionic surfactant is chosen from mono- and glycerol distearate, mono- and ethylene glycol distearate, diethylene glycol mono- and distearate and propylene glycol mono- and distearate, and ethoxylated stearyl alcohol with an ethoxylation number between 2 and 21, 'and any mixture thereof.
5. Composition selon l'une quelconque des revendications 1 à 4, caractérisée en ce que la concentration pondérale dudit agent tensioactif non ionique principal est comprise entre 1 et 15% du poids total de la composition.5. Composition according to any one of claims 1 to 4, characterized in that the weight concentration of said main nonionic surfactant is between 1 and 15% of the total weight of the composition.
6. Composition selon la revendication 1, caractérisée en ce que la fraction externe est définie dans l'espace de Hansen par le paramètre partiel de polarité δp et le paramètre partiel de liaison hydrogène δh, à l'intérieur d'un parallélépipède dont la projection dans le plan δp, δh est une surface rectangulaire ayant une longueur sur l'axe δh de 16 (cal/cm3)12, soit 32,64 (J/cm3)12, à partir du point d'origine 0, et une largeur sur l'axe δp de 12 (cal/cm3)l , soit 24,48 (J/cm3)'/2, à partir du point d'origine 0.6. Composition according to claim 1, characterized in that the external fraction is defined in the Hansen space by the partial parameter of polarity δp and the partial parameter of hydrogen bonding δh, inside a parallelepiped whose projection in the plane δp, δh is a rectangular surface having a length on the axis δh of 16 (cal / cm 3 ) 12 , that is 32.64 (J / cm 3 ) 12 , from the point of origin 0, and a width on the axis δp of 12 (cal / cm 3 ) l , i.e. 24.48 (J / cm 3 ) ' / 2 , from the point of origin 0.
7. Composition selon la revendication 1, caractérisée en ce que ledit solvant est choisi parmi les dialkylesters, tels que les mélanges d'adipate, de glutarate et de succinats, mais aussi le dibutylphtalate, parmi les monoalkylesters tels que le lactate d'éthyle, le lactate de butyle et autres esters de l'acide lactique, le carbonate de propylène, le carbonate d'éthylène, parmi les esters d'éthers de l'éthylène glycol, les esters d'éthers du propylène glycol, tels que l'acétate de propylène glycol méthyléther, le diacetate de propylène glycol, les méthoxy-esters et les éthoxy-ester comme l'éthoxy-3- propionate d'éthyle (en abrégé EEP) , parmi les éthers de 1 'éthylène-glycol et les éthers du propylène glycol, peu solubles ou insolubles dans l'eau, tels que les éthers mono-n-butyliques du propylène glycol, du dipropylène glycol et du tripropylène glycol, l'éther mono-t-butylique du propylène glycol (en abrégé PTB) , et 1 'éther monophénylique du propylène glycol, parmi les cétones telles que la méthylphénylcétone, la N-méthyl-pyrrolidone, la méthylisobutylcétone et la cyclohexanone, parmi les acides organiques tels que les mono- et di-acides carboxyliques et les acides polyfonctionnels tels que l'acide oxalique, l'acide citrique, l'acide lactique, et parmi les bases organiques telles que les alkylamines, ou les mélanges de ceux-ci.7. Composition according to Claim 1, characterized in that the said solvent is chosen from dialkyl esters, such as mixtures of adipate, glutarate and succinates, but also dibutylphthalate, among monoalkyl esters such as ethyl lactate, butyl lactate and other esters of lactic acid, propylene carbonate, ethylene carbonate, among esters of ethylene glycol ethers, esters of propylene glycol ethers, such as propylene glycol methyl ether acetate, propylene glycol diacetate, methoxy esters and ethoxy esters such as ethoxy-3-propionate d 'ethyl (abbreviated as EEP), among ethers of ethylene glycol and ethers of propylene glycol, poorly soluble or insoluble in water, such as mono-n-butyl ethers of propylene glycol, dipropylene glycol and tripropylene glycol, propylene glycol mono-t-butyl ether (abbreviated PTB), and propylene glycol monophenyl ether, among ketones such as methylphenylketone, N-methyl-pyrrolidone, methylisobutylketone and cyclohexanone , among the s organic acids such as mono- and di-carboxylic acids and polyfunctional acids such as oxalic acid, citric acid, lactic acid, and among organic bases such as alkylamines, or mixtures thereof this.
8. Composition selon la revendication 1, caractérisée en ce que le cosolvant est choisi parmi les dérivés du glycol comprenant le mono-, le di- et le tri- et autres polyéthylèneε et polypropylènes glycol, et l'hexylène glycol, parmi le glycérol, le sorbitol, le dextrose et le saccharose, parmi les éthers de l' éthylène- glycol et les éthers du propylène-glycol, solubles ou moyennement solubles dans l'eau, tels que le propylène glycol méthyl éther, le dipropylène glycol méthyl éther et le tripropylène glycol méthyl éther, parmi les alcools aliphatiques et aromatiques tels que l'alcool benzylique, parmi l'acétone, la N-méthyl-2-pyrrolidone, la 7- butyrolactone, ainsi que l'eau, et tout mélange de ceux- ci. 8. Composition according to Claim 1, characterized in that the cosolvent is chosen from glycol derivatives comprising mono-, di- and tri- and other polyethylene and polypropylene glycol, and hexylene glycol, from glycerol, sorbitol, dextrose and sucrose, among the ethylene glycol ethers and the propylene glycol ethers, soluble or moderately soluble in water, such as propylene glycol methyl ether, dipropylene glycol methyl ether and tripropylene glycol methyl ether, among aliphatic and aromatic alcohols such as benzyl alcohol, among acetone, N-methyl-2-pyrrolidone, 7-butyrolactone, as well as water, and any mixture thereof .
9. Composition selon les revendications 7 et 8, caractérisée en ce que ledit solvant est un diméthylester ou un mélange de diméthylesters, et ledit cosolvant est choisi parmi le monopropylene glycol, le glycérol, l'hexylène glycol ou un polypropylène glycol de poids moléculaire moyen supérieur ou égal à 400.9. Composition according to Claims 7 and 8, characterized in that said solvent is a dimethylester or a mixture of dimethylesters, and said cosolvent is chosen from monopropylene glycol, glycerol, hexylene glycol or a polypropylene glycol of average molecular weight greater than or equal to 400.
10. Composition selon la revendication 1, caractérisée en ce que la concentration pondérale de la fraction de solvant est comprise entre 1 et 90% du poids total de la composition.10. Composition according to claim 1, characterized in that the weight concentration of the solvent fraction is between 1 and 90% of the total weight of the composition.
11. Composition selon la revendication 1, caractérisée en ce que la fraction tensioactive comprend en outre au moins un autre agent tensioactif choisi parmi premièrement les agents tensioactifs non-ioniques différents dudit agent tensioactif non ionique principal, tels que les alcools éthoxylés, les nonylphénols éthoxylés, les alkylpolyglucosides, les amides gras éthoxylés ou non, les esters de sorbitanne éthoxylés ou non, les alcanolamides, deuxièmement les agents tensioactifs anioniques, tels que las alkylsulfates, les alkyléthersulfates, les alkylsulfosuccinates et les esters phosphoriques d'alcool gras éthoxylé, troisièmement les agents tensioactifs amphotères, tels que les dérivés des alkylbétaïnes, et quatrièmement les agents tensioactifs cationiques.11. Composition according to claim 1, characterized in that the surfactant fraction further comprises at least one other surfactant chosen firstly from nonionic surfactants other than said main nonionic surfactant, such as ethoxylated alcohols, ethoxylated nonylphenols , alkylpolyglucosides, fatty amides, ethoxylated or not, sorbitan esters ethoxylated or not, alkanolamides, secondly anionic surfactants, such as alkylsulfates, alkylethersulfates, alkylsulfosuccinates and phosphoric esters of ethoxylated fatty alcohol, thirdly amphoteric surfactants, such as alkylbetaine derivatives, and fourthly cationic surfactants.
12. Composition selon la revendication 11, caractérisée en ce que ledit autre agent tensioactif est un mélange d'agents tensioactifs possédant une chaîne carbonée en C12~c l8' c'est-à-dire en C12, C14, C16 et C18, avec une proportion pondérale en agents tensioactifs en Cig-Cig/ au moins équivalente à celle en agents tensioactifs en C12-C14.12. Composition according to claim 11, characterized in that said other surfactant is a mixture of surfactants having a carbon chain C 12 ~ c l8 'that is to say C 12 , C 14 , C 16 and C 18 , with a weight proportion of Cig-Cig / surfactants / at least equivalent to that in C 12 -C 14 surfactants.
13. Composition selon la revendication 11, caractérisée en ce que ledit autre agent tensioactif est choisi parmi les agents tensioactifs ayant une chaîne carbonée en C 8~C 12' éthoxylés ou non, les agents tensioactifs éthoxylés possédant un indice d 'éthoxylation compris entre 1 et 5.13. Composition according to claim 11, characterized in that said other surfactant is chosen from surfactants having a carbon chain C 8 ~ C 12 'ethoxylated or not, the agents ethoxylated surfactants having an ethoxylation index of between 1 and 5.
14. Composition selon l'une quelconque des revendications 11 à 13, caractérisée en ce que la concentration pondérale des agents tensioactifs différents de l'agent tensioactif principal est au plus égale à 50%.14. Composition according to any one of claims 11 to 13, characterized in that the weight concentration of surfactants other than the main surfactant is at most equal to 50%.
15. Composition selon les revendications 12 et 14, caractérisée en ce qu'elle comprend :15. Composition according to claims 12 and 14, characterized in that it comprises:
- 1 à 30% en poids d'esters dibasiques, - 1 à 30% en poids de monopropylene glycol ou glycérol,- 1 to 30% by weight of dibasic esters, - 1 to 30% by weight of monopropylene glycol or glycerol,
- 1 à 15% en poids de mono- ou distéarate de glycérol- 1 to 15% by weight of glycerol mono- or distearate
- 1 à 30% en poids de tensioactifs, non ioniques différents de l'agent tensioactif principal, et/ou anioniques et/ou amphotères, et1 to 30% by weight of nonionic surfactants other than the main surfactant, and / or anionic and / or amphoteric, and
- de l'eau.- some water.
16. Composition selon les revendications 13 et 14, caractérisée en ce qu'elle comprend : - une fraction solvante dans une proportion de 1 à16. Composition according to Claims 13 and 14, characterized in that it comprises: - a solvent fraction in a proportion of 1 to
90% en poids,90% by weight,
- 1 à 15% en poids de mono- ou distéarate de glycérol,- 1 to 15% by weight of glycerol mono- or distearate,
- 1 à 50% en poids d'agents tensioactifs différents de l'agent tensioactif principal- 1 to 50% by weight of surfactants different from the main surfactant
- 0 à 88 % en poids d'eau.- 0 to 88% by weight of water.
17. Crème lavante pour les mains caractérisée en ce qu'elle incorpore à titre de principe actif une composition selon l'une quelconque des revendications 12, 14 et 15.17. Washing hand cream characterized in that it incorporates as active principle a composition according to any one of claims 12, 14 and 15.
18. Crème selon la revendication 17, caractérisée en ce que la fraction tensioactive de la composition possède un pouvoir solvant complémentaire vis-à-vis des corps gras. 18. Cream according to claim 17, characterized in that the surfactant fraction of the composition has a complementary solvent power vis-à-vis fatty substances.
19. Préparation décapante caractérisée en ce qu'elle incorpore à titre de principe actif une composition selon l'une quelconque des revendications 13, 14 et 16. 19. Stripper preparation characterized in that it incorporates as active ingredient a composition according to any one of claims 13, 14 and 16.
PCT/FR1995/000994 1994-08-02 1995-07-24 Cleaning or scouring compositions, and preparations containing them WO1996004342A1 (en)

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EP1803803A2 (en) * 2005-12-30 2007-07-04 Lam Research Corporation Cleaning compounds and method and system for using the cleaning compound
US7309684B2 (en) 2005-05-12 2007-12-18 The Lubrizol Corporation Oil-in-water emulsified remover comprising an ethoxylated alcohol surfactant
ITMI20121992A1 (en) * 2012-11-23 2014-05-24 Allegrini S P A COMPOSITION FOR THE REMOVAL OF DYES OR SUBSTANCES

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EP0294041A2 (en) * 1987-06-04 1988-12-07 Minnesota Mining And Manufacturing Company Aqueous-based composition for removing coatings
EP0389829A1 (en) * 1989-03-13 1990-10-03 BASF Corporation Water based paint stripper and varnish remover for wood
WO1992018600A1 (en) * 1991-04-10 1992-10-29 Minnesota Mining And Manufacturing Company Low voc cleaning compositions and methods
WO1993007227A1 (en) * 1991-10-11 1993-04-15 Minnesota Mining And Manufacturing Company Aqueous based composition containing organic solvents for removing coatings
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7176174B2 (en) 2003-03-06 2007-02-13 The Lubrizol Corporation Water-in-oil emulsion
US7309684B2 (en) 2005-05-12 2007-12-18 The Lubrizol Corporation Oil-in-water emulsified remover comprising an ethoxylated alcohol surfactant
EP1803803A2 (en) * 2005-12-30 2007-07-04 Lam Research Corporation Cleaning compounds and method and system for using the cleaning compound
EP1803803A3 (en) * 2005-12-30 2012-08-01 Lam Research Corporation Cleaning compounds and method and system for using the cleaning compound
ITMI20121992A1 (en) * 2012-11-23 2014-05-24 Allegrini S P A COMPOSITION FOR THE REMOVAL OF DYES OR SUBSTANCES

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FR2723377A1 (en) 1996-02-09
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CA2196545A1 (en) 1996-02-15
FR2723377B1 (en) 1997-01-10

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