EP0710274B1 - Nettoyants a haut pouvoir mouillant - Google Patents
Nettoyants a haut pouvoir mouillant Download PDFInfo
- Publication number
- EP0710274B1 EP0710274B1 EP94924746A EP94924746A EP0710274B1 EP 0710274 B1 EP0710274 B1 EP 0710274B1 EP 94924746 A EP94924746 A EP 94924746A EP 94924746 A EP94924746 A EP 94924746A EP 0710274 B1 EP0710274 B1 EP 0710274B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acids
- group
- weight
- formulations
- general formula
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
- 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
-
- 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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
-
- 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
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
Definitions
- the invention relates to powdery, pasty or liquid agents for cleaning and / or degreasing hard surfaces, for example metallic surfaces, but in particular surfaces made of organic polymers, for example paints and coatings, but in particular surfaces made of halogenated polyolefins such as polyvinyl chloride.
- the agent is characterized by a combination of active ingredients consisting of amino acids, carboxylic acids or their salts and nonionic surfactants.
- the agents can be used as industrial cleaners (as neutral cleaners or as alkaline cleaners) as well as for vehicle and company cleaning.
- DE-A-27 12 900 describes a method for cleaning metals by spraying.
- the cleaning is carried out at pH values between 7.5 to 11, preferably 8.5 to 10, with solutions which A) soluble salts, preferably alkanolamine salts of aromatic carboxylic acids and / or branched and / or straight-chain aliphatic carboxylic acids with 6 to 12 C atoms, B) one or more nonionic surfactants, C) one or more surface-active quaternary ammonium compounds.
- A) soluble salts, preferably alkanolamine salts of aromatic carboxylic acids and / or branched and / or straight-chain aliphatic carboxylic acids with 6 to 12 C atoms B) one or more nonionic surfactants, C) one or more surface-active quaternary ammonium compounds.
- GB-A-2 231 580 describes cleaning agents which are particularly intended for the sanitary area. They have pH values between 6.0 and 8.0 and contain: A) 0.1 to 20% by weight of an anionic and / or nonionic surface-active agent, B) hydroxycarboxylic acids or their salts C) amminocarboxylic acids or their salts and D ) 0.1 to 20 wt .-% of an alkylene glycol alkyl ether as a solvent.
- aminocarboxylic acids are not understood to mean free amino acids Have NH 2 groups. Rather, the term aminocarboxylic acid here stands for carboxylic acids with a tertiary amino function, for example nitrilotriacetic acid or ethylenediaminetetraacetic acid.
- DE-A-32 06 350 relates to a liquid detergent mixture which has a suitable viscosity at the time of its use. It is specifically intended as a shampoo. Its main components consist of ammonium alkyl sulfates, alkylenediamine carboxylic acid derivatives and 0.1 to 5% by weight of a carboxylic acid, a salt of the carboxylic acid, an amino acid or one of the salts of the amino acid.
- the carboxylic acid is selected from fatty acids with 1 to 8 carbon atoms, dicarboxylic acids with 2 to 7 carbon atoms, hydroxycarboxylic acids or unsaturated, polybasic carboxylic acids.
- the amino acid is to be selected from neutral amino acids, acidinamino acids, basic amino acids, oxyamino acids, imino acids or sulfur-containing amino acids.
- the amino acids glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophanic acid, sarcosine, beta-alanine, gamma-aminobutyric acid, epsilon-aminocaproic acid, glutamic acid, aspartic acid, cysteic acid, homocysteic acid, lysine, ornithine, homo-arginine, are particularly preferred , Tyrosine, threonine, proline, hydroxyproline, cystine, cysteine or methionine.
- WO 92/01 778 discloses a manufacturing process for a detergent powder for textile washing, in which the acid form of an anionic surfactant is continuously neutralized with alkali metal hydroxide.
- This document is related to the present invention by adding an alpha-aminodicarboxylic acid selected from the group consisting of glutamic acid, aspartic acid, aminomalonic acid, aminoadipic acid and 2-amino-2-methylpentanedioic acid or salts thereof.
- Sodium glutamate is particularly preferred.
- Optional components of the detergent mixture are also nonionic, cationic, amphoteric or zwitterionic surfactants.
- These detergents can furthermore contain carboxylates, C 10 -C 18 alkyl monocarboxylates, ie soaps, being particularly mentioned.
- DE-A-19 42 236 describes detergents, washing aids and cleaning agents which have a particularly good dissolving power for protein-containing soiling in that they have sulfur-free, 4-11 carbon atoms and optionally containing a further carboxyl and / or amino group containing amino acids or their salts.
- the preferred amino acids for this are glutamic acid, aspartic acid, histidine, arginine and lysine.
- the detergents also contain protein-splitting enzymes.
- Further constituents of the agents are the usual detergent constituents of detergents, washing aids and cleaning agents, in particular anionic and / or nonionic surfactants and builder substances.
- active ingredients according to the invention described below, consisting of amino acids, certain carboxylic acids and nonionic surfactants, and their special mixing ratios is not anticipated or suggested by this.
- German patent application P 43 19 578.4 of the applicant discloses powdery to granular detergents for textile washing which contain anionic and / or nonionic surfactants as well as zeolite and / or one or more silicates from the group of amorphous and crystalline, layered alkali metal silicates and as a result are characterized in that they additionally contain sulfur-free, 2 to 11 carbon atoms and optionally an additional carboxyl and / or amino group having amino acids and / or their salts.
- the amino acids are preferably selected from glycine, alanine, valine, leucine, isoleucine and their salts.
- These detergents can additionally contain carboxylic acid derivatives in the form of peracids as bleaching agents or soaps as foam inhibitors.
- C12-C24 fatty acid soaps are particularly preferred as soaps.
- These detergents for textile washing therefore contain the typical detergent constituents called zeolite and / or layered alkali silicates.
- German patent application P 43 19 798.1 discloses agents for the mechanical cleaning of dishes, the 1% by weight aqueous solution of which has a pH of 8 to 12, preferably 9 to 11, containing water-soluble builder components and bleaching agents based on oxygen, and thereby characterized in that 0.5 to 60 wt .-%, preferably 10 to 50 wt .-% of one or more amino acids are contained as alkali carriers.
- Alanine, valine, leucine, isoleucine and in particular glycine are mentioned as amino acids. The task of these amino acids and their salts is to serve as readily biodegradable alkali carriers.
- DE-A-19 64 792 also relates - as an additional application to DE-A-19 42 236 cited above - to protein-detergents, washing aids and cleaning agents, the amino acids mentioned in the main application being wholly or partly by sulfur-free amino acids with 2 or 3 carbon atoms or their salts, in particular glycerol, are replaced.
- the usual detergent constituents of detergents as mentioned above in the main application, may be considered as further constituents, including soaps from fatty acids with 10 to 22 carbon atoms and nonionic surfactants.
- DE-A-25 10 245 describes universal household cleaners for all types of hard surfaces which, in addition to anionic surfactants selected from organic surface-active detergent-effective sulfuric acid reaction products, and polypeptides or protein hydrolyzates preferably contain nonionic surfactants.
- the object of the invention is to provide improved cleaning agents for cleaning / degreasing technical surfaces, for example metallic surfaces, but in particular plastic surfaces.
- Surfaces made of non-polar plastics such as those made of polyvinyl chloride (PVC) or polypropylene, can only be cleaned or degreased with great effort because of their comparatively poor wetting behavior.
- PVC polyvinyl chloride
- the formulation that the acids mentioned under a) and b) may be present as such or in the form of their anions means that these acids must be in a water-soluble form, be it that they themselves have sufficient water solubility, that they are contained in the agent in the form of water-soluble salts.
- Particularly suitable as water-soluble salts are the alkali metal salts, preferably the sodium salts, of these acids.
- the anions can be used as ammonium salts or as salts with substituted ammonium ions.
- Alkanolammonium ions are preferably chosen as substituted ammonium ions.
- the naturally occurring alpha-amino acids or amino acid derivatives are generally chiral with respect to the carbon atom carrying the amino group and are in the L form.
- the chiral L-amino acids offer no particular advantage for the technical application according to the invention, they are preferably used as natural or nature-identical active ingredients.
- amino acids in the form of their racemates or in optically active form can be used, for example: glycine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophanic acid, sarcosine, beta-alanine, gamma-aminobutyric acid, epsilon-aminocaproic acid, glutamine, glutamic acid, aspartic acid , Lysine, ornithine, arginine, serine, homoserine, tyrosine, threonine, proline, hydroxyproline, aminomalonic acid, aminoadipic acid and 2-amino-2-methylpentanedioic acid. Particularly good results are obtained with glutamic acid.
- the agents can also contain amino acid precursors which can convert into the amino acids under the conditions of use of the detergent bath.
- amino acid precursors are, for example, oligopeptides or protein hydrolyzates, lactams such as, for example, epsilon-caprolactam or anhydrides of polybasic amino acids.
- the carboxylic acids of group b) can be represented by the general formula (II) R 6 -COOH (II) where R 6 is an aliphatic, linear or branched hydrocarbon radical having 5 to 9 carbon atoms and 0 or a double bond.
- R 6 is an aliphatic, linear or branched hydrocarbon radical having 5 to 9 carbon atoms and 0 or a double bond.
- the saturated carboxylic acids, hexanoic acid (caproic acid), octanoic acid (caprylic acid) and decanoic acid (capric acid) are particularly preferred.
- Branched saturated carboxylic acids in particular 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid and 2,2-dimethyloctanoic acid, also offer particular technical advantages.
- the non-ionic surfactants should be selected so that they comply with the legal requirements (detergent law) with regard to their biodegradability. To limit the tendency of the detergent to foam, it is recommended that the cloud points of the nonionic surfactants be below the intended working temperatures of 10 to 70 ° C. The foaming tendency of the cleaning solutions can be further suppressed by adding so-called mixed ethers even at low working temperatures, for example at temperatures between 10 and 25 ° C.
- the mixed ethers which can be used are end-capped ethoxylation products of fatty alcohols of the general formula R'-O- (EO) n -R ", in which R 'is an alkyl or alkenyl radical having 6-18 C atoms, R" is an alkyl radical having 4-8 C atoms and n represent a number from 2-6.
- R' is an alkyl or alkenyl radical having 6-18 C atoms
- R" is an alkyl radical having 4-8 C atoms
- n represent a number from 2-6.
- the homolog distribution of the EO chain can be conventional or narrow.
- Corresponding products and their effective amounts used (10-2500 ppm, preferably 50-500 ppm in the ready-to-use cleaning solution) are described in more detail, for example, in the published documents DE-A-37 27 378 and DE-A-39 35 374.
- composition of the agents according to the invention is preferably adjusted so that it contains the amino acids or amino acid derivatives from group a) or their anions in amounts between 0.4 and 4% by weight. and or the carboxylic acids from group b) or their anions in amounts between 2 and 7% by weight and or contain the nonionic surfactants from group c) in amounts between 5 and 10% by weight.
- the cleaners can be formulated as aqueous concentrates, as pumpable pastes or as powders.
- solutions of the constituents according to the invention from groups a), b) and c) are prepared in water in the above-mentioned proportions.
- the aqueous concentrates may contain other auxiliaries customary for cleaners, such as builder substances, further surfactants, polymers and / or complexing agents.
- the auxiliaries mentioned are added in powder form to the active compound combination according to the invention in groups a), b) and c) in such proportions that the total mixture contains the active compounds in groups a), b) and c) in the stated quantitative ranges .
- Pastes contain the active ingredients of groups a), b) and c) in the specified quantity ranges in addition to liquid or solid auxiliaries from the groups mentioned above and enough water to produce a pumpable paste.
- the agents according to the invention fall under the group of neutral cleaners or are alkaline cleaners.
- neutral cleaners are defined as cleaners whose 0.5-2% aqueous solution has a pH in the range of about 6-9.5. At higher pH values, the cleaners are referred to as alkaline cleaners.
- the cleaning solution have demulsifying properties. This means that oily impurities are very easily removed from the surfaces to be degreased, but that these impurities do not form a stable emulsion in the aqueous cleaning solution, but rather - at the working temperature or, if necessary, after temperature adjustment and / or dilution - as an oily phase on the aqueous Float the cleaner. The oil phase can then be easily removed from the cleaning solution, so that the service life of the cleaning bath can be extended considerably.
- the demulsifying properties of the cleaning / degreasing agents according to the invention are particularly evident when diluting the cleaning solutions.
- ammonium compounds of the formula (IV) are suitable as cationic surfactants: suitable which contain one, two or three unsubstituted or hydroxyl-substituted linear or branched carbon chains.
- Ammonium compounds of the general formula R a R b R c R d N + X - are preferably used, in which at least one, preferably two of the radicals R are unsubstituted or optionally substituted by a hydroxyl group with 1-2 carbon atoms and at least one of the remaining radicals R are unsubstituted or optionally substituted by a hydroxyl group in the 2-position straight-chain or branched alkyl groups with at least 10 carbon atoms and the anion X from the group hydroxide, chloride, bromide, sulfate , Nitrate, phosphate, preferably borate, is selected.
- ammonium salts are used as cationic surfactants in which R a and R b are methyl, R c is methyl, 2-hydroxyethyl, benzyl, 2-hydroxydodecyl or 2-hydroxyhexadecyl and R d 2-hydroxydodecyl, 2-hydroxyhexadecyl, lauryl, hexadecyl or stearyl .
- R a R b R c R d N + X - are also used as cationic surfactants, in which R a , R b and R c are (ethylene oxide) n groups, where n is 1-6, R d Is alkyl radical with 10-20 carbon atoms and X are anions from the group carboxylate, in particular benzoate, hydroxide, chloride, bromide, sulfate, nitrate, phosphate, preferably borate.
- Alkylpyridinium salts of the general formula C 5 H 5 N + -RX - are also used as cationic surfactants, in which R is an alkyl radical with 10-20 carbon atoms, preferably with 12-16 carbon atoms, and X anions from the group carboxylate, in particular benzoate, hydroxide, Chloride, bromide, sulfate, nitrate, phosphate, preferably borate.
- nitrogen-containing polymers which can be cationically modified or converted into the corresponding ammonium salts either by protonation or alkylation, generally methylation, of nitrogen are suitable as cationic polymers or cationically modified polymers.
- the degree of cationic modification is different and depends on the neutral starting polymer, on the corresponding acid for protonation or on the corresponding alkylation agent.
- cationic polymers which are used alone or together with cationic surfactants in the composition according to the invention are protonated quaternary acrylamides, N, N-dialkylaminoalkyl acrylates, dialkylamines or vinylpyridine, and methylated quaternary polymers such as polydiallyldimethylammonium chloride or poly-N-methylvinylpyridinium chloride.
- the molecular weights of the cationic polymers used in the agent according to the invention are between 5 ⁇ 10 4 and 5 ⁇ 10 7 , preferably between 7.5 ⁇ 10 4 and 5 ⁇ 10 6 .
- the invention also includes agents which select one or more complexing agents from at least one of the groups d) hydroxypolycarboxylic acids, e) nitrogen-containing mono- or polycarboxylic acids, f) mono- or diphosphonic acids, g) aminophosphonic acids, h) phosphonopolycarboxylic acids, and water-soluble salts Contain sodium, potassium or ammonium salts of the acids of groups d) to h) in amounts with respect to the free acids between 0.01 and 15 wt .-%.
- the agents according to the invention can be used without further alkaline builder substances. For demanding cleaning tasks, however, it is advisable to increase the cleaning effect with alkaline builder substances.
- the builders commonly used for alkaline cleaners are suitable for this.
- the agents according to the invention also include those which contain one or more builder substances selected from at least one of the groups i) mono-, di- or triethanolamine or their cations, k) alkali metal hydroxides, 1) silicates, preferably metasilicates, m) carbonates, n) Oligo- or polycarboxylates, o) ortho- or polyphosphates, p) borates, in amounts between 0.01 and 94.8% by weight, the anions of groups 1) to p) being in the form of their water-soluble salts, preferably ammonium - Or alkali metal salts, in particular as Li, Na or K salts.
- the invention further comprises processes for cleaning and / or degreasing hard surfaces, characterized in that the surfaces are brought into contact with 2 to 50% by weight aqueous solutions of the compositions by dipping or spraying at temperatures between 10 and 70 ° C.
- the expedient concentrations to be set or the dilutions to be selected depend on whether the agents according to the invention are used as powders, as pastes rich in active substances or as more or less highly concentrated aqueous concentrates.
- the preferred procedure is to use 2 to 10% by weight aqueous solutions in the case of powdery compositions, 2 to 15% by weight aqueous solutions when using pasty compositions and 5 to 15% by weight aqueous solutions when using liquid compositions Uses solutions.
- the invention also relates to processes in which the aqueous cleaning solution, in addition to the agents according to the invention, additionally comprises one or more anionic surfactants selected from at least one of the groups q) alkyl sulfates with a linear or branched alkyl radical having 10 to 18 carbon atoms, r) alkyl polyglycol ether sulfates with a linear or branched alkyl radical with 10 to 18 carbon atoms and 1 to 6 -CH 2 -CH 2 -O- groups in the molecule, s) alkylarylsulfonates with an alkylbenzene radical with a linear or branched alkyl group with 7 to 9 carbon atoms in Contains amounts between 0.01 and 3% by weight, the surfactant anions preferably being in the form of the alkali metal salts, in particular the sodium salts.
- the cleaning / degreasing agents and cleaning methods according to the invention can generally be used for the fields of work of industrial cleaners, including vehicle and operational cleaning.
- Their advantage of high wetting power is particularly evident when the surfaces to be degreased are surfaces made from organic polymers. Examples of this are painted surfaces or surfaces made of polycarbonates or polyurethanes.
- the cleaners were formulated as powder products or as liquid aqueous concentrates in deionized water (Examples 1-3). To prepare the degreasing baths, the powders or the concentrates were dissolved or diluted with city water (18 ° German hardness) to the concentrations given in the tables.
- Triethanolamine 18.2 sodium 2.0 2-ethylhexanoic acid 8.5 L-glutamic acid 1.3 Octylphosphonic acid 1.0 Nitrilotri (methylenephosphonic acid) 3.0 Sodium hydroxide 6.5 C 10/12 alcohol mix x 6 EO x 8 PO 7.0 water 52.5
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Claims (16)
- Agents pulvérulents, pâteux ou liquides pour le nettoyage et/ou le dégraissage des surfaces dures, contenanta) 0,2 à 12 % en poids d'un ou de plusieurs acides mono- ou dicarboxyliques monoaminés ou diaminés aliphatiques ou aromatiques ou de monoamides d'acides dicarboxyliques monoaminés de la formule générale (I)R1 peut représenter sur chaque atome de C, indépendamment l'un de l'autre, H, OH, CH3 ou C2H5,R2 peut représenter sur chaque atome de C, indépendamment l'un de l'autre, H, CH3 ou C2H5,R3 correspond à H, à CH3 ou à C2H5,R4 peut représenter sur chaque atome de C, indépendamment l'un de l'autre, H, OH, CH3 ou C2H5,R5 peut représenter sur chaque atome de C, indépendamment l'un de l'autre, H, CH3 ou C2H5 etX est l'hydrogène, un radical homo- ou hétérocyclique, de préférence un phényle, C(O)OH ou C(O)NH2 et à la condition que b > 0, en outre NH2, NH-C(=NH)-NH2, NH-C(=O)-NH2,ou les anions de ceux-ci,b) 1 à 12 % en poids d'un ou de plusieurs acides carboxyliques, qui répondent à la formule générale (Il),
R6-COOH (II)
dans laquelle R6 représente un radical hydrocarboné aliphatique, linéaire ou ramifié comportant 5 à 9 atomes de carbone avec zéro ou une double liaison, ou représente un groupe R7-C6H4-C(O)-CH=CH-, dans lequel R7 représente un radical alkyle linéaire ou ramifié comportant 8 à 14 atomes de carbone, ou les anions de ceux-ci,c) 4 à 15 % en poids d'un ou de plusieurs tensioactifs non ioniques, sélectionnés parmi le groupe des alcools gras éthoxylé et/ou éthoxylés et propoxylés de la formule générale (III)
R8-O-(EO)X-(PO)Y-H (III)
dans laquelleR8 représente un radical alkyle linéaire ou ramifié comportant 6 à 14 atomes de C,x correspond à un nombre dans l'intervalle de 2 à 10 ety est un nombre dans l'intervalle de 0 à 8,EO représente un groupe -CH2-CH2-O etPO correspond à un groupe -CH(CH3)-CH2-O- et le reste pour donner 100 % étant constitué d'eau et/ou d'adjuvants, de préférence sélectionnés parmi des substances adjuvantes, d'autres tensioactifs, des polymères et des agents complexants. - Agents selon la revendications 1, caractérisés en ce que dans la formule générale (I) des acides aminés ou des dérivés d'acides aminés du groupe a), R1, R2, R3, R4 et R5 représente chacun l'hydrogène.
- Agents selon une des revendications 1 et 2, caractérisés en ce que dans la formule générale (I) a = O.
- Agents selon la revendication 3, caractérisés en ce que dans la formule générale (I), R3 représente l'hydrogène.
- Agents selon une ou plusieurs des revendications 1 à 4, caractérisés en ce que les acides aminés ou les dérivés d'acides aminés de la formule générale (I) sont chiraux en ce qui concerne l'atome de carbone portant le groupe amino et sont présents, de préférence, sous la forme L.
- Agents selon une ou plusieurs des revendications 1 à 5, caractérisés en ce que sont mis en oeuvre comme dérivés d'acides aminés de la formule générale (I), des oligopeptides, des hydrolysats de protéines, des lactames ou des anhydrides d'acides aminés polybasiques.
- Agents selon une ou plusieurs des revendications 1 à 6 caractérisés en ce qu'ils contiennent les acides aminés ou les dérivés d'acides aminés du groupe a) ou les anions de ceux-ci, en proportions comprises entre 0,4 et 4 % en poids et/ou les acides carboxyliques du groupe b) ou les anions de ceux-ci, en quantités comprises entre 2 et 7 % en poids, et/ou les tensioactifs non ioniques du groupe c), en proportions comprises entre 5 et 10 % en poids.
- Agents selon une ou plusieurs des revendications 1 à 7, caractérisés en ce qu'ils contiennent des tensioactifs cationiques, des bétaïnes et/ou des polymères à modification cationique, en proportions comprises entre 0,01 et 3 % en poids.
- Agents selon une ou plusieurs des revendications 1 à 8, caractérisés en ce qu'ils contiennent un ou plusieurs agents complexants sélectionnés parmi au moins un des groupes d) acides hydroxypolycarboxyliques, e) acides mono- ou polycarboxyliques azotés, f) acides mono- ou disphosphoniques, g) acides aminophosphoniques, h) acides phosphonopolycarboxyliques, ainsi que les sels solubles dans l'eau, de préférence les sels de sodium, de potassium ou d'ammonium des acides des groupes d) à h), dans des proportions par rapport aux acides libres, comprises entre 0,01 et 15 % en poids.
- Agents selon une ou plusieurs des revendications 1 à 9, caractérisés en ce qu'ils contiennent une ou plusieurs substances adjuvantes sélectionnées parmi au moins un des groupes i) mono-, di- ou triéthanolamines ou cations de celles-ci, k) hydroxydes de métaux alcalins, I) silicates, de préférence métasilicates, m) carbonates, n) oligo- ou polycarboxylates, o) ortho- ou polyphosphates, p) borates, en proportions comprises entre 0,01 et 94,8 % en poids, les anions des groupes l) à p) étant présents sous la forme de leurs sels solubles dans l'eau, de préférence comme sels d'ammonium ou de métaux alcalins, en particulier comme sels de lithium, de sodium ou de potassium.
- Agents selon une ou plusieurs des revendications 1 à 10, caractérisés en ce qu'ils contiennent en plus 0,05 à 14,5 % en poids d'éthers mixtes de la formule générale R'-O-(EO)n-R", dans laquelle R' représente un radical alkyle ou alcényle comportant 6 à 18 atomes de C, R" correspond à un radical akyle comportant 4 à 8 atomes de C et n est un nombre de 2 à 6.
- Agents selon une ou plusieurs des revendications 1 à 11, caractérisés en ce que l'acide aminé du groupe a) est l'acide glutamique.
- Procédé de nettoyage et/ou de dégraissage des surfaces dures, caractérisé en ce que l'on met en contact les surfaces avec des solutions aqueuses à 2 à 50 % en poids des agents selon une ou plusieurs des revendications 1 à 12, par immersion ou pulvérisation à des températures comprises entre 10 et 70 °C.
- Procédé selon la revendication 13, caractérisé en ce que l'on utilise pour des agents pulvérulents, des solutions aqueuses à 2 à 10 % en poids, en cas d'emploi d'agents pâteux, des solutions aqueuses à 2 à 15 % en poids et en cas de mise en oeuvre d'agents liquides, des solutions aqueuses à 5 à 15 % en poids.
- Procédé selon une des revendications 13 et 14 ou selon les deux, caractérisé en ce que la solution nettoyante contient en plus un ou plusieurs surfactifs anioniques, sélectionnés parmi au moins un des groupes q) alkylsulfates avec un radical alkyle linéaire ou ramifié comportant 10 à 18 atomes de C, r) alkylpolyglycol-éthersulfates avec un radical alkyle linéaire ou ramifié comportant 10 à 18 atomes de C et 1 à 6 groupes -CH2-CH2-O- dans la molécule, s) alkylarylsulfonates avec un radical alkylbenzène avec un groupe alkyle linéaire ou ramifié comportant 7 à 9 atomes de C, en proportions comprises entre 0,01 et 3 % en poids, les anions tensioactifs étant présents de préférence sous la forme de sels de métaux alcalins, en particulier de sels de sodium.
- Procédé selon une ou plusieurs des revendications 13 à 15, caractérisé en ce que les surfaces sont des surfaces en polymères organiques, de préférence des surfaces laquées et/ou des surfaces en polycarbonates, en polyuréthanes, en polyoléfines, en polyoléfines halogénées et en particulier, en chlorure de polyvinyle.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4324396A DE4324396A1 (de) | 1993-07-21 | 1993-07-21 | Reinigungsmittel mit hohem Benetzungsvermögen |
DE4324396 | 1993-07-21 | ||
PCT/EP1994/002285 WO1995003389A1 (fr) | 1993-07-21 | 1994-07-12 | Nettoyants a haut pouvoir mouillant |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0710274A1 EP0710274A1 (fr) | 1996-05-08 |
EP0710274B1 true EP0710274B1 (fr) | 1997-10-01 |
Family
ID=6493315
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94924746A Expired - Lifetime EP0710274B1 (fr) | 1993-07-21 | 1994-07-12 | Nettoyants a haut pouvoir mouillant |
Country Status (7)
Country | Link |
---|---|
US (1) | US5935920A (fr) |
EP (1) | EP0710274B1 (fr) |
AT (1) | ATE158813T1 (fr) |
DE (2) | DE4324396A1 (fr) |
DK (1) | DK0710274T3 (fr) |
ES (1) | ES2109012T3 (fr) |
WO (1) | WO1995003389A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3156475B1 (fr) | 2015-10-16 | 2018-06-06 | Hans Georg Hagleitner | Concentré de nettoyage liquide |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19719606C2 (de) * | 1997-05-09 | 1999-02-18 | Henkel Kgaa | Feststoffzubereitungen |
DE19842053A1 (de) * | 1998-09-15 | 2000-03-23 | Bayer Ag | Verwendung von Polyasparaginsäuren in Reinigerformulierungen mit abrasiver Wirkung |
US6428814B1 (en) * | 1999-10-08 | 2002-08-06 | Elan Pharma International Ltd. | Bioadhesive nanoparticulate compositions having cationic surface stabilizers |
US6559116B1 (en) | 1999-09-27 | 2003-05-06 | The Procter & Gamble Company | Antimicrobial compositions for hard surfaces |
DE10007323A1 (de) * | 2000-02-17 | 2001-08-23 | Bode Chemie Gmbh & Co Kg | Reinigunsmittel für medizinische Instrumente |
US6514458B1 (en) * | 2000-02-25 | 2003-02-04 | Ge Betz, Inc. | Method for removing microbes from surfaces |
EP1259115A1 (fr) * | 2000-02-25 | 2002-11-27 | BetzDearborn Inc | Procede permettant d'accentuer l'activite biocide |
DE102004057623A1 (de) | 2004-11-29 | 2006-06-01 | Henkel Kgaa | Metallreiniger mit Polyethylenimin |
DE102006018216B4 (de) | 2006-04-18 | 2008-09-25 | Chemetall Gmbh | Verfahren zum demulgierenden Reinigen von metallischen Oberflächen |
US8093200B2 (en) | 2007-02-15 | 2012-01-10 | Ecolab Usa Inc. | Fast dissolving solid detergent |
DE102007000501A1 (de) * | 2007-10-15 | 2009-04-16 | Chemetall Gmbh | Reinigerzusammensetzung für metallische Oberflächen |
EP2138437A1 (fr) | 2008-06-27 | 2009-12-30 | Kba-Giori S.A. | Système d'inspection pour contrôler la qualité de feuilles imprimées |
EP2305785A1 (fr) | 2009-10-02 | 2011-04-06 | Unilever N.V. | Utilisation d'un composé carboxylique ou amino en tant qu'aide au nettoyage pour les surfaces dures et procédé de nettoyage desdites surfaces dures |
US8389463B2 (en) * | 2009-11-09 | 2013-03-05 | Ecolab Usa Inc. | Enhanced dispensing of solid compositions |
WO2011105449A1 (fr) * | 2010-02-23 | 2011-09-01 | ライオン株式会社 | Agent de nettoyage des métaux |
US20130096045A1 (en) | 2011-10-12 | 2013-04-18 | Ecolab Usa Inc. | Moderately alkaline cleaning compositions for proteinaceous and fatty soil removal at low temperatures |
CN104903433A (zh) * | 2012-12-20 | 2015-09-09 | 荷兰联合利华有限公司 | 去污组合物 |
KR20180066109A (ko) | 2015-10-07 | 2018-06-18 | 엘리멘티스 스페셜티즈, 인크. | 습윤제 및 소포제 |
JP2019531375A (ja) * | 2016-08-25 | 2019-10-31 | エコラボ ユーエスエー インコーポレイティド | アミノ酸を含む洗浄組成物および使用方法 |
WO2022018779A2 (fr) * | 2020-07-19 | 2022-01-27 | University Of Petra | Composition liquide moussante sûre pour soins personnels |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL33876A0 (en) * | 1969-03-28 | 1970-04-20 | Miles Lab | Anti-tarnish composition for metal surfaces and process for its use |
DE1942236A1 (de) * | 1969-08-20 | 1971-03-04 | Henkel & Cie Gmbh | Eiweissloesende Wasch-,Waschhilfs- und Reinigungsmittel |
DE1964792A1 (de) * | 1969-12-24 | 1971-07-01 | Henkel & Cie Gmbh | Eiweissloesende Wasch-,Waschhilfs- und Reinigungsmittel |
FR2264085B1 (fr) * | 1974-03-15 | 1976-12-17 | Procter & Gamble Europ | |
DE2712900C2 (de) * | 1977-03-24 | 1986-04-10 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur Reinigung von Metallen im Spritzverfahren |
US4412943A (en) * | 1981-02-23 | 1983-11-01 | Kao Soap Co., Ltd. | Liquid detergent composition |
JPS6115815A (ja) * | 1984-06-29 | 1986-01-23 | Lion Corp | 毛髪用化粧料 |
DE3727378A1 (de) * | 1987-08-17 | 1989-03-02 | Henkel Kgaa | Schaumdrueckende zusaetze in schaumarmen reinigungsmitteln |
JPH0299599A (ja) * | 1988-10-07 | 1990-04-11 | Sumitomo Light Metal Ind Ltd | 空調用アルミニウム製熱交換器の洗浄剤 |
JPH0699703B2 (ja) * | 1989-05-12 | 1994-12-07 | 花王株式会社 | 浴室用液体洗浄剤組成物 |
DE3935374A1 (de) * | 1989-10-24 | 1991-04-25 | Henkel Kgaa | Alkylpolyethylenglykolether als schaumdrueckende zusaetze fuer reinigungsmittel |
US5066425A (en) * | 1990-07-16 | 1991-11-19 | The Procter & Gamble Company | Formation of high active detergent particles |
JP3170724B2 (ja) * | 1992-03-11 | 2001-05-28 | 味の素株式会社 | 洗浄剤組成物 |
DE4319578A1 (de) * | 1993-06-14 | 1994-12-15 | Henkel Kgaa | Waschmittel, enthaltend Aminosäuren und/oder deren Salze |
DE4319798A1 (de) * | 1993-06-15 | 1994-12-22 | Henkel Kgaa | Geschirrspülmittel mit verringerter Belagsbildungsneigung |
US5415813A (en) * | 1993-11-22 | 1995-05-16 | Colgate-Palmolive Company | Liquid hard surface cleaning composition with grease release agent |
US5573702A (en) * | 1993-11-22 | 1996-11-12 | Colgate-Palmolive Co. | Liquid cleaning compositions with grease release agent |
BR9408124A (pt) * | 1993-11-22 | 1997-08-05 | Colgate Palmolive Co | Composição em microemulsão composição de limpeza para superficies duras para todos os fins detergente líquido para serviços leves e composição detergente líquida |
US5486307A (en) * | 1993-11-22 | 1996-01-23 | Colgate-Palmolive Co. | Liquid cleaning compositions with grease release agent |
-
1993
- 1993-07-21 DE DE4324396A patent/DE4324396A1/de not_active Withdrawn
-
1994
- 1994-07-12 US US08/583,083 patent/US5935920A/en not_active Expired - Fee Related
- 1994-07-12 WO PCT/EP1994/002285 patent/WO1995003389A1/fr active IP Right Grant
- 1994-07-12 DE DE59404229T patent/DE59404229D1/de not_active Expired - Fee Related
- 1994-07-12 ES ES94924746T patent/ES2109012T3/es not_active Expired - Lifetime
- 1994-07-12 AT AT94924746T patent/ATE158813T1/de not_active IP Right Cessation
- 1994-07-12 DK DK94924746.4T patent/DK0710274T3/da active
- 1994-07-12 EP EP94924746A patent/EP0710274B1/fr not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3156475B1 (fr) | 2015-10-16 | 2018-06-06 | Hans Georg Hagleitner | Concentré de nettoyage liquide |
Also Published As
Publication number | Publication date |
---|---|
EP0710274A1 (fr) | 1996-05-08 |
US5935920A (en) | 1999-08-10 |
ES2109012T3 (es) | 1998-01-01 |
ATE158813T1 (de) | 1997-10-15 |
DE59404229D1 (de) | 1997-11-06 |
DE4324396A1 (de) | 1995-01-26 |
DK0710274T3 (da) | 1998-05-11 |
WO1995003389A1 (fr) | 1995-02-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0710274B1 (fr) | Nettoyants a haut pouvoir mouillant | |
EP1817398B1 (fr) | Produit nettoyant pour metaux contenant un polyethylene imine | |
CH657372A5 (de) | Stabilisiertes enzymhaltiges fluessiges reinigungsmittel. | |
DE202014011351U1 (de) | Mischungen von Enantiomeren und Reinigungsmittelzusammensetzungen | |
EP0986631B1 (fr) | Detergent faiblement moussant | |
EP1445301B1 (fr) | Dispersions aqueuses liquides détergentes | |
WO1993023522A1 (fr) | Concentres de nettoyants alcalins susceptibles d'etre pompes | |
EP0282863A2 (fr) | Concentrés de nettoyage liquides alcalins | |
DE102010055742A1 (de) | Zusammensetzungen enthaltend sekundäres Paraffinsulfonat und Alkoholalkoxylat | |
EP0721496B1 (fr) | Decolorants et desinfectants | |
EP1306423A2 (fr) | Composition nettoyante aqueuse comprenant des agents tensioactifs et ayant un pouvoir séchant amelioré pour le nettoyage des surfaces dures, specialement pour la vaisselle | |
EP0728180B1 (fr) | Adjuvant pour le lavage des bouteilles en verre et son utilisation pour reduire la corrosion du verre | |
DE102010055743A1 (de) | Zusammensetzungen enthaltend sekundäres Paraffinsulfonat und Alkoholalkoxylat | |
EP0755428B1 (fr) | Utilisation d'ethoxylates d'amines grasses dans des nettoyants aqueux pour surfaces dures | |
DE19803054A1 (de) | Bleich- und Desinfektionsmittel | |
DE19530833A1 (de) | Oberflächenaktive Zubereitungen | |
DE4334368C2 (de) | Schwach schäumende polymerfreie Reinigungsmittel | |
EP4025109B1 (fr) | Robot nettoyeur comprenant un tissu de nettoyage et un moyen de nettoyage | |
EP0658187B1 (fr) | Nettoyants alcalins liquides contenant des disels d'acides sulfo-oleiques et leur utilisation | |
WO2012084149A1 (fr) | Compositions contenant un sulfonate de paraffine secondaire et une tétrahydroxypropyl éthylène diamine | |
WO1993006200A1 (fr) | Polyalkyleneglycols d'alcools gras avec distribution restreinte des homologues dans des nettoyeurs par immersion faiblement moussants | |
WO2000011962A1 (fr) | Procede de nettoyage de chauffe-lait |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19960115 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE |
|
17Q | First examination report despatched |
Effective date: 19960604 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 158813 Country of ref document: AT Date of ref document: 19971015 Kind code of ref document: T |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
ET | Fr: translation filed | ||
REF | Corresponds to: |
Ref document number: 59404229 Country of ref document: DE Date of ref document: 19971106 |
|
ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN P. & C. S.N.C. |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2109012 Country of ref document: ES Kind code of ref document: T3 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19971222 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19980703 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19980707 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19980709 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 19980713 Year of fee payment: 5 Ref country code: AT Payment date: 19980713 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19980720 Year of fee payment: 5 Ref country code: DE Payment date: 19980720 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19980722 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19980728 Year of fee payment: 5 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19980914 Year of fee payment: 5 |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990712 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990712 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990713 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19990730 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990731 Ref country code: FR Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19990731 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990731 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990802 |
|
BERE | Be: lapsed |
Owner name: HENKEL K.G.A.A. Effective date: 19990731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000201 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19990712 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
EUG | Se: european patent has lapsed |
Ref document number: 94924746.4 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20000201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000503 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20020603 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050712 |