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).

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• 1994
  • 1994-08-02 FR FR9409828A patent/FR2723377B1/fr not_active Expired - Fee Related
• 1995
  • 1995-07-24 AU AU30820/95A patent/AU3082095A/en not_active Abandoned
  • 1995-07-24 CA CA 2196545 patent/CA2196545A1/fr not_active Abandoned
  • 1995-07-24 WO PCT/FR1995/000994 patent/WO1996004342A1/fr not_active Application Discontinuation
  • 1995-07-24 EP EP95926421A patent/EP0773978A1/de not_active Withdrawn

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