EP1254948A1 - Tensioactifs gemini - Google Patents
Tensioactifs gemini Download PDFInfo
- Publication number
- EP1254948A1 EP1254948A1 EP02009407A EP02009407A EP1254948A1 EP 1254948 A1 EP1254948 A1 EP 1254948A1 EP 02009407 A EP02009407 A EP 02009407A EP 02009407 A EP02009407 A EP 02009407A EP 1254948 A1 EP1254948 A1 EP 1254948A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- alkyl
- surfactants
- contain
- gemini surfactants
- 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.)
- Granted
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- 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
- C11D1/721—End blocked 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
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
-
- 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
Definitions
- the invention relates to gemini surfactants, optionally in conjunction with detergents and cleaning agents usual ingredients, optionally with other nonionic surfactants and anionic surfactants and the use of such gemini surfactants to improve the wetting behavior and Compatibility with plastics, for the simplified manufacture of solid cleaners and as foam-suppressing surfactant in rinse aid formulations.
- Means for rinsing and cleaning hard, non-textile surfaces should mostly develop a small foam volume when used, which will decrease significantly within a few minutes.
- Means of this kind have been known for a long time and are established on the market. These are essentially aqueous surfactant solutions of various types with or without the addition of builders, solubilizers (hydrotropes) or solvents. To prove the effectiveness at the beginning of the cleaning work, the consumer wants a certain amount of foam in the application solution, but the foam should collapse quickly so that once cleaned surfaces do not have to be wiped off.
- agents of the type mentioned are usually mixed with low-foaming nonionic surfactants.
- liquid or solid rinse aid which can be added separately, or already in ready-to-use form with the detergent and / or regeneration salt together ("2 in 1", “3 in 1”, eg in the form of tabs and powders), ensures that the water runs off the dishes as completely as possible, so that the different surfaces are residue-free and shiny at the end of the wash program.
- Common detergents and cleaning agents are mixtures of nonionic surfactants, solubilizers, organic acids and solvents, water as well as preservatives and fragrances.
- the task of the surfactants in these agents is to influence the interfacial tension of the water so that it can run off the wash ware in a thin, coherent film, so that no water drops, streaks or films remain during the subsequent drying process (so-called wetting effect or wetting behavior) ).
- these surfactants also have to dampen the foam that arises from food residues in the dishwasher. Since rinse aids mostly contain acids to improve the clear dry effect, the surfactants used must also be relatively insensitive to hydrolysis against acids.
- Combined products from dishwashing detergent with built-in rinse aid are being used more and more both in the household and in the commercial sector.
- the rinse aid was previously metered into household dishwashers and released into the rinsing chamber at just under 40 ° C - 65 ° C after the pre-rinse and cleaning cycle.
- the rinse aid is released from the combined dishwashing detergents (eg "2 in 1" tabs or powder) with a time delay to the detergent and is thus dosed into the rinsing chamber.
- the commercial dishwashers work with only one cleaning fleet, which is only through Adding the rinsing solution from the previous rinsing process is renewed. So it takes place during no complete water exchange takes place during the entire washing program. Therefore, the flushing and Detergents also have a foam-suppressing effect, being temperature-stable with a strong one Temperature drop of 85-35 ° C and also be sufficiently stable against alkali and active chlorine.
- the object of the present invention was to provide detergents and cleaning agents which at the same time have good foam and cleaning behavior, but in particular very good drainage behavior, ie an improvement in the wetting behavior on plastic surfaces and high material compatibility, in particular with plastics. In addition, it should be easier to prepare solid detergent formulations.
- the problem was solved by using selected surfactants of the gemini surfactant type.
- the invention relates to gemini surfactants of the formula (I), R-CHOH-CH 2 [OCH 2 CH 2 ] XO-CH 2 -CHOH-R in which pure linear or branched alkyl and / or alkenyl radical having 4 to 22, preferably 8 to 18, in particular 8 to 12 carbon atoms and x is 5 to 90, preferably 10 to 45 and in particular 12 to 35.
- Gemini surfactants are generally prepared by reacting 1,2-epoxyalkanes (CH 2 CHO-R), where R is a linear or branched, saturated or unsaturated alkyl and / or alkenyl radical, with polyols.
- polyol is the collective name for polyhydric alcohols or polyalkylene glycols, i.e. H. as an organic compound containing at least two hydroxyl groups in the mole.
- the polyalkylene glycols also include reaction products of polyhydric alcohols To understand alkoxylation reagents such as ethylene oxide and propylene oxide.
- polyethylene glycol HO- [OCH 2 CH 2 ] x-OH is used as the polyol.
- Gemini surfactants of the formula (I) are particularly preferred, where x is from 10 to 45, preferably from 12 to 35.
- Gemini surfactants of the formula (I) are very particularly preferred, where R is a linear or branched alkyl radical having 8 to 12 carbon atoms.
- Gemini surfactants of the formula (I) are further preferred, where R is a linear alkyl radical with 8 to 12 carbon atoms, especially with 10 carbon atoms.
- gemini surfactants of the formula (I) are preferred, which thereby are characterized in that they are at least 80% by weight, preferably 85 to 100% by weight, in particular Contain 95 to 100 wt.% Gemini surfactants, in which all free hydroxyl groups of Polyethylene glycols are sealed with 1,2-epoxyalkane units.
- detergents and cleaning agents which contain the gemini surfactants according to the invention and further ingredients customary in detergents and cleaning agents.
- these customary ingredients can be alkyl and / or alkenyl oligoglycosides, other nonionic surfactants, anionic surfactants, builders, enzymes and other auxiliaries and additives.
- Rinsing and cleaning agents which contain gemini surfactants of the formula (I) in which x is from 5 to 90, preferably from 10 to 45, in particular from 12 to 35 and R for a linear or branched alkyl and / or alkenyl radical are very particularly preferred 4 to 22 carbon atoms.
- the rinsing and cleaning agents according to the invention contain alkyl and / or alkenyl oligoglycosides of the formula (II).
- R 1 O- [G] P where R 1 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10.
- the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
- the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligo glucosides .
- the alkyl radical R 1 can be derived from primary saturated alcohols .
- Typical examples are butanol-1, capron, ⁇ nanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, cetyl alcohol , palmity alcohol , heptadecanol-1, stearyl alcohol, isostearecanol alcohol -1, arachidyl alcohol, heneicosanol-1, and behenyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
- the alkenyl radical R 1 can be derived from primary unsaturated alcohols .
- unsaturated alcohols are undecen-1-ol, oleyl alcohol, elaidyl alcohol, ricinol alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidone alcohol, eruca alcohol, brassidyl alcohol, palmoleyl alcohol, petroselinyl alcohol, arachyl alcohol, and their technical mixtures, which can be obtained as described above, and their technical mixtures.
- Alkyl or alkenyl radical R 1 which are derived from primary alcohols having 6 to 16 carbon atoms are preferred . Particularly suitable are alkyl oligoglucosides of chain length C 8 -C 10 , which are obtained as a preliminary step in the separation of technical C 8 -C 18 coconut fatty alcohol by distillation and which may be contaminated with a proportion of less than 6% by weight of C 12 alcohol, as well as alkyl oligoglucosides based on technical C 9/11 oxo alcohols.
- the alkyl or alkenyl radical R 1 can also be derived from primary alcohols having 12 to 14 carbon atoms.
- Alkyl and / or alkenyl oligoglycosides of the formula (II) are preferably used, where p represents numbers from 1 to 3 and R 1 represents an alkyl radical having 6 to 16 carbon atoms.
- the washing-up and cleaning agents according to the invention contain 0.01 to 25% by weight, preferably 0.025 to 20% by weight and in particular 0.1 to 15% by weight of gemini surfactants of the formula (I), calculated as active substance, based on the Medium.
- Active substance is defined here as the mass of surfactant (calculated as 100% pure substance) contained in the agent.
- the washing-up and cleaning agents according to the invention contain 0.01 to 30% by weight, preferably 0.1 to 20% by weight and in particular 0.2 to 15% by weight of alkyl and / or alkenyl oligoglycosides of the formula (II) calculated as Active substance, based on the funds.
- the detergents and cleaning agents according to the invention can contain further nonionic surfactants.
- Typical examples of non-ionic surfactants are alkoxylates of alkanols, end-capped alkoxylates of alkanols without free OH groups, alkoxylated fatty acid lower alkyl esters, amine oxides, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerol ethers, fatty glucide amides, mixed glycidyl amides, mixed glycidyl amides, mixed glycidyl amides, mixed glycidyl amides, mixed glycidyl amides, and mixed acid amides vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, and polysorbates.
- nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
- the further nonionic surfactants are preferably selected from the group formed by alkoxylates of alkanols, in particular fatty alcohol polyethylene glycol / polypropylene glycol ether (FAEO / PO) of the formula (III) or fatty alcohol polypropylene glycol / polyethylene glycol ether (FAPO / EO) of the formula (IV), end-capped Alkoxylates of alkanols, especially end-capped fatty alcohol polyethylene glycol / polypropylene glycol ether or end-capped fatty alcohol polypropylene glycol / polyethylene glycol ether, and fatty acid lower alkyl esters and amine oxides.
- alkoxylates of alkanols in particular fatty alcohol polyethylene glycol / polypropylene glycol ether (FAEO / PO) of the formula (III) or fatty alcohol polypropy
- the rinsing and cleaning agents according to the invention contain fatty alcohol polyethylene glycol / polypropylene glycol ether of the formula (III) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms, n1 is a number from 1 to 10 , and m represents 0 and R 7 represents hydrogen.
- R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 C atoms
- n1 is a number from 1 to 10
- m represents 0
- R 7 represents hydrogen.
- These are addition products of 1 to 10 moles of ethylene oxide with monofunctional alcohols.
- the alcohols described above, such as fatty alcohols, oxo alcohols and Guerbet alcohols are suitable as alcohols. Of such alcohol ethoxylates, those are also suitable which have a narrow homolog distribution.
- R 6 for an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms
- n1 for a number from 2 to 7
- m for a number of 3 to 7
- R 7 represents hydrogen.
- the end group-capped compounds of the formula (III) are capped with an alkyl group having 1 to 8 carbon atoms (R 7 ).
- R 7 alkyl group having 1 to 8 carbon atoms
- Such compounds are often referred to in the literature as mixed ethers.
- Suitable representatives are methyl group-capped compounds of the formula (III) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n1 is a number from 2 to 7, m is a number from 3 to 7 and R 7 represents a methyl group.
- Such compounds can easily be prepared by reacting the corresponding non-end-capped fatty alcohol polyethylene glycol / polypropylene glycol ether with methyl chloride in the presence of a base.
- Suitable representatives of alkyl-capped compounds are those of the formula (III) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n1 is a number from 5 to 15, m is 0 and R 7 represents an alkyl group with 4 to 8 carbon atoms.
- the end group closure is preferably carried out with a straight-chain or branched butyl group by the corresponding fatty alcohol polyethylene glycol ether with n-butyl chloride or with tert. Butyl chloride is reacted in the presence of bases.
- end-capped fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (IV) may be present.
- Such connections are described, for example, in German published patent application DE-A1- 43 23 252.
- Particularly preferred representatives of the compounds of the formula (IV) are those in which R 8 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, q is a number from 1 to 5, r is a number of 1 to 6 and R 9 represents hydrogen.
- R 8 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms
- q is a number from 1 to 5
- r is a number of 1 to 6
- R 9 represents hydrogen.
- These are preferably addition products of 1 to 5 mol of propylene oxide and of 1 to 6 mol of ethylene oxide with monofunctional alcohols, which have already been described as suitable in connection with the gemini surfactants.
- Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V) R 10 CO- (OCH 2 CHR 11 ) w OR 12 in which R 10 CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R 11 is hydrogen or methyl, R 12 is a linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands.
- Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid, and technical grade mixtures and erucas.
- the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
- amine oxides Compounds of the formula (VI) and / or can be used as amine oxides .
- the preparation of the amine oxides of the formula (VI) starts from tertiary fatty amines which have at least one long alkyl radical and is oxidized in the presence of hydrogen peroxide.
- R 13 represents a linear or branched alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms
- R 14 and R 15 independently of one another are R 13 or, if appropriate hydroxy-substituted alkyl radical having 1 to 4 carbon atoms.
- Amine oxides of the formula (VI) are preferably used, in which R 13 and R 14 are C 12/14 and C 12/18 cocoalkyl radicals and R 15 is a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (VI) in which R 13 represents a C 12/14 or C 12/18 cocoalkyl radical and R 14 and R 15 have the meaning of a methyl or hydroxyethyl radical.
- alkylamido -amine oxides of the formula (VII)
- the alkylamido radical R 23 CONH being obtained by the reaction of linear or branched carboxylic acids, preferably having 6 to 22, preferably having 12 to 18, carbon atoms, in particular from C 12/14 or C 12/18 - fatty acids with amines.
- R 24 represents a linear or branched alkylene group having 2 to 6, preferably 2 to 4 carbon atoms and R 14 and R 15 have the meaning given in formula (VI) .
- the further nonionic surfactants can be present in the detergents and cleaning agents according to the invention in amounts of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, in particular 1 to 8% by weight, calculated as the active substance, based on the means.
- the rinsing and cleaning agents according to the invention can contain anionic surfactants .
- anionic surfactants are soaps, alkylbenzene sulfonates, secondary alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerin ether sulfates, mono ether sulfate sulfate, hydroxymischogether sulfate, fatty acid ether sulfate sulfates, Mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarc
- the anionic surfactants are preferably selected from the group consisting of alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, monoglyceride (ether) sulfates and alkane sulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates and linear alkyl benzene sulfonates.
- Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (VIII) R 16 O-SO 3 X in which R 16 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
- the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
- Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred.
- ether sulfates are known anionic surfactants which are produced on an industrial scale by SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
- SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
- ether sulfates are suitable which follow the formula (IX) R 17 O- (CH 2 CH 2 O) a SO 3 X in which R 17 represents a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, a for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with caprone alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, aryl alcohol alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, o
- the ether sulfates can have both a conventional and a narrow homolog distribution. It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C 12/14 or C 12/18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
- Alkylbenzenesulfonates preferably follow the formula (X), R 16 Ph-SO 3 X in which R 18 represents a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph a phenyl radical and X an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- R 18 represents a branched but preferably linear alkyl radical having 10 to 18 carbon atoms
- Ph a phenyl radical an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used.
- Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry.
- the usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)].
- the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE 4204700 A1 (Henkel)].
- Overviews of the chemistry of the monoglyceride sulfates are, for example, by AK Biswas et al. in J.Am.Oil.Chem.Soc. 37 , 171 (1960) and FU Ahmed J.Am.Oil.Chem.Soc. 67 , 8 (1990) .
- the monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (XI), in which R 19 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, c, d and e in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal.
- Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide.
- Monoglyceride sulfates of the formula (XI) are preferably used in which R 19 CO stands for a linear acyl radical having 8 to 18 carbon atoms.
- Alkane sulfonates are taken to mean compounds of the formula (XII).
- R 20 and R 21 represent alkyl radicals, where R 20 and R 21 together should not have more than 50 carbon atoms.
- the washing-up and cleaning agents can expediently contain 0.01 to 20% by weight, preferably 0.25 to 15% by weight, in particular 0.4 to 10% by weight, of anionic surfactants , calculated as the active substance, based on the agent.
- the rest which is missing by 100% by weight, can be auxiliary substances and additives as well as water.
- the rinsing and cleaning agents according to the invention can be used as customary ingredients or auxiliaries and additives, for example solubilizers such as cumene sulfonate, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, diethylene glycol, propylene glycol monobutyl ether, polyethylene or polypropylene glycol ether with molecular weights from 600 to 1,500,000. preferably with a molecular weight of 400,000 to 800,000, or in particular butyl diglycol.
- Abrasive materials such as quartz or wood flour or polyethylene friction bodies can also be contained.
- the detergents and cleaning agents can contain cationic surfactants or biocides, for example glucoprotamine.
- Suitable builders are zeolites, phyllosilicates, phosphates and ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and its salt, and inorganic phosphonic acids.
- bleaching agents sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H 2 O 2 -producing peracid salts of peracids such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 0.1 to 40% by weight.
- the use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred.
- the use of sodium percarbonate in conjunction with alkyl and / or alkenyl oligoglycosides is also preferred.
- Suitable enzymes are those from the class of proteases, lipase, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus lichenformis and Strptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentes are preferably used. Their proportion can be about 0.1 to 6, preferably 0.2 to 2% by weight. The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition.
- the agents can contain further enzyme stabilizers .
- enzyme stabilizers 0.5 to 1% by weight sodium formate can be used.
- proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
- boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
- foam inhibitors When used in the machine washing process, it can be advantageous to add conventional foam inhibitors to the agents.
- Suitable foam inhibitors contain, for example, known organoolysiloxanes and / or paraffins or waxes.
- Foam regulators such as soap, fatty acids, in particular coconut fatty acid and palm kernel fatty acid, may also be included.
- thickeners which can be used are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used.
- the latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50 to 10% by weight of maleic acid.
- the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably between 50,000 to 120,000, based on the free acid.
- Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above 1,000,000 are particularly suitable. Examples of these are polymers obtainable under the name Carbopol® 940 and 941.
- the crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, particularly preferably in amounts of 0.2 to 0.7% by weight.
- detergents and cleaning agents are preferred which contain 0.1 to 15, preferably 0.5 to 12% by weight of surfactants which contain gemini surfactants of the formula (I), in particular those based on Polyethylene glycol, where x is 10 to 45, R is a linear alkyl radical with 8 to 12 carbon atoms.
- the agents according to the invention contain 5 to 90, preferably 10 to 80 wt.% Builders, 0.1 to 6 wt.% Detergent enzyme, optionally 0.1 to 40, preferably 0.5 to 30 wt.% Bleaches and auxiliaries and additives , % By weight is to be understood in relation to the average.
- Powdery or tablet-shaped dishwashing detergents are very particularly preferred, which can also have a rinse aid function at the same time.
- Another object of the present invention is the use of gemini surfactants Formula (I) for rinsing and cleaning hard surfaces, preferably in the household and industrial and institutional area.
- gemini surfactants of the formula (I) according to the invention is particularly preferred for Improvement of the wetting behavior in detergents and cleaning agents, preferably on hard ones Surfaces, especially in machine dishwashers, that contain rinse aid.
- gemini surfactants of the formula (I) for improving the Plastic compatibility in detergents and cleaning agents, especially in machine dishwashers, that contain rinse aid.
- gemini surfactants of the formula (I) in combination with alkyl and / or Alkenyl oligoglycosides in the cleaning areas listed so far.
- gemini surfactants of the formula (I) according to the invention are very particularly preferred in combination with the other surfactants already described, for the simplified production of solid detergent formulations.
- the gemini surfactants according to the invention can because of their higher Melting points easier in detergent and cleaning agent formulations, especially in solid cleaners be incorporated.
- gemini surfactants according to formula (I) as a foam-suppressant Surfactant in detergents and cleaning agents.
- the inventive ones are distinguished Gemini surfactants, in addition to their foam-suppressing effect and high tolerance, in particular compared to plastic, due to their higher melting points. This makes them particularly suitable for simplified production of solid formulations.
- the gemini surfactants also dissolve, due to their higher melting points, later in the cleaning liquor and unfold with a time delay, and in higher concentration their effect. This effect can be particularly advantageous in machine Dishwashing detergents with built-in rinse aid can be used.
- Plastic test specimens measuring 20 x 5 cm are used to evaluate the wetting properties first cleaned with 1% NaOH and then with isopropanol. The test specimens pretreated in this way are then immersed in the solution to be tested and immediately removed again. The evaluation takes place visually by compiling a ranking list or on a scale from 1 to 5. 5 means that spontaneous tearing of the liquid film occurs and the wetting is completely removed. grade 5 is obtained when using water. The grade 1 means complete wetting of the Plastic surface with a smooth flow of the liquid film.
- PP polypropylene
- PE polyethylene
- PC polycarbonate
- Table 2 shows the melting points of the gemini surfactants. Melting points / areas ° C 2-hydroxydodecyl ether-PEG 600-2-hydroxydodecyl ether 27 2-hydroxydodecyl ether-PEG 1000-2-hydroxydodecyl ether 36 2-hydroxydodecyl ether-PEG 1500-2-hydroxydodecyl ether 43 C 12/14 FA 5EO + 4PO liquid at room temperature Poly Tergent SLF-18B-45 27-32
- Gemini surfactants with melting points above 35 ° C. are used to formulate combination products made from dishwashing detergent and rinse aid ("2 in 1". "3 in 1").
- Sample recipes for machine dishwashing detergents 1 2 3 Active substance in% 2-hydroxydodecyl ether-PEG 600-2-hydroxydodecyl ether 14 2-hydroxydodecyl ether-PEG 1000-2-hydroxydodecyl ether 14 2-hydroxydodecyl ether-PEG 1500-2-hydroxydodecyl ether 14 Sodium tripolyphosphate 45 45 45 45 45 45 Sodium perborate 12 12 12 soda 15 15 15 Water glass 2.0 10 10 10 10 10 Enzymes (protease, amylase) 2 2 2 Other ingredients ad 100
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10121724A DE10121724A1 (de) | 2001-05-04 | 2001-05-04 | Geminitenside |
DE10121724 | 2001-05-04 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1254948A1 true EP1254948A1 (fr) | 2002-11-06 |
EP1254948B1 EP1254948B1 (fr) | 2004-07-14 |
Family
ID=7683621
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02009407A Expired - Fee Related EP1254948B1 (fr) | 2001-05-04 | 2002-04-25 | Tensioactifs gemini |
Country Status (4)
Country | Link |
---|---|
US (1) | US6794345B2 (fr) |
EP (1) | EP1254948B1 (fr) |
DE (2) | DE10121724A1 (fr) |
ES (1) | ES2225684T3 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1288281A2 (fr) * | 2001-08-07 | 2003-03-05 | Cognis Deutschland GmbH & Co. KG | Tensioactifs gémini et polyéthylène glycol |
EP1306422A1 (fr) * | 2001-10-23 | 2003-05-02 | Cognis Deutschland GmbH & Co. KG | Produits solides de lavage, de rincage et de nettoyage |
EP1764408A1 (fr) | 2005-09-14 | 2007-03-21 | Cognis IP Management GmbH | Mélanges des agents tensio-actifs pour l'utilisation dans des composition de nettoyage |
WO2009100855A2 (fr) * | 2008-02-14 | 2009-08-20 | Cognis Ip Management Gmbh | Utilisation de substances tensioactives dans des nettoyants |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10121724A1 (de) * | 2001-05-04 | 2002-11-07 | Cognis Deutschland Gmbh | Geminitenside |
DE10121722A1 (de) * | 2001-05-04 | 2002-11-07 | Cognis Deutschland Gmbh | Geminitenside in Klarspülmitteln |
DE10121723A1 (de) * | 2001-05-04 | 2002-11-07 | Cognis Deutschland Gmbh | Geminitenside |
DE10162023A1 (de) * | 2001-12-18 | 2003-07-03 | Cognis Deutschland Gmbh | Mischungen aus Geminitensiden und Fettalkoholalkoxylaten in Klarspülmitteln |
US8470305B2 (en) | 2002-06-04 | 2013-06-25 | The Procter & Gamble Company | Shampoo containing a gel network |
US8349301B2 (en) | 2002-06-04 | 2013-01-08 | The Procter & Gamble Company | Shampoo containing a gel network |
DE10320154B3 (de) * | 2003-05-06 | 2005-02-17 | Huf Hülsbeck & Fürst Gmbh & Co. Kg | Vorrichtung zum Sperren der Lenkspindel eines Kraftfahrzeugs |
US7199090B2 (en) | 2003-09-29 | 2007-04-03 | Ethena Healthcare Inc. | High alcohol content gel-like and foaming compositions comprising an alcohol and fluorosurfactant |
DE102004062775A1 (de) | 2004-12-21 | 2006-06-29 | Stockhausen Gmbh | Alkoholischer Pumpschaum |
CN104739665A (zh) | 2005-03-07 | 2015-07-01 | 戴博全球保健有限公司 | 含有有机硅表面活性剂的高醇含量发泡组合物 |
US20100311633A1 (en) * | 2007-02-15 | 2010-12-09 | Ecolab Usa Inc. | Detergent composition for removing fish soil |
US8093200B2 (en) | 2007-02-15 | 2012-01-10 | Ecolab Usa Inc. | Fast dissolving solid detergent |
US8580860B2 (en) * | 2007-02-23 | 2013-11-12 | Gojo Industries, Inc. | Foamable alcoholic composition |
US20080274932A1 (en) * | 2007-05-04 | 2008-11-06 | Ecolab Inc. | Composition for in situ manufacture of insoluble hydroxide when cleaning hard surfaces and for use in automatic warewashing machines and methods for manufacturing and using |
MX2009013704A (es) | 2009-12-15 | 2011-06-15 | Mexicano Inst Petrol | Nuevos surfactantes geminales, proceso de obtencion y uso como inhibidores de corrosion multifuncionales. |
MX2014006223A (es) | 2014-05-23 | 2015-11-23 | Inst Mexicano Del Petróleo | Liquidos zwitterionicos geminales ramificados, proceso de obtencion y uso como modificadores de la mojabilidad con propiedades reductoras de la viscosidad. |
CN112760345A (zh) * | 2019-11-01 | 2021-05-07 | 南京盛德生物科技研究院有限公司 | 一种酶法制备环氧烷烃的工艺 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0300305A2 (fr) * | 1987-07-18 | 1989-01-25 | Henkel Kommanditgesellschaft auf Aktien | Utilisation d'éthers hydroxyalkylpolyéthylenglycoliques comme produits de rinçage pour le lavage mécanique de la vaisselle |
DE19513391A1 (de) * | 1995-04-08 | 1996-10-10 | Henkel Kgaa | Bi- und multifunktionelle Mischether |
WO1998015346A1 (fr) * | 1996-10-04 | 1998-04-16 | Rhodia Inc. | Amelioration d'agents antisalissures a l'aide de tensioactifs jumeles |
EP0884298A2 (fr) * | 1997-06-12 | 1998-12-16 | Henkel Kommanditgesellschaft auf Aktien | Tensioactifs géminés, mélange de tensioactifs et compositions détergentes |
WO1999027047A1 (fr) * | 1997-11-22 | 1999-06-03 | Henkel-Ecolab Gmbh & Co. Ohg | Produit pour le nettoyage de surfaces dures |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2522287C2 (de) * | 1975-05-20 | 1981-09-24 | Degussa Ag, 6000 Frankfurt | Mittel zur antistatischen Ausrüstung von thermoplastischen Kunststoffen |
DE4038478A1 (de) | 1990-12-03 | 1992-06-04 | Henkel Kgaa | Verfahren zur herstellung von partialglyceridsulfaten |
DE4038477A1 (de) | 1990-12-03 | 1992-06-04 | Henkel Kgaa | Verfahren zur kontinuierlichen herstellung von partialglyceridsulfaten |
DE4204700A1 (de) | 1992-02-17 | 1993-08-19 | Henkel Kgaa | Verfahren zur abtrennung anorganischer salze |
DE4321022A1 (de) * | 1993-06-24 | 1995-01-05 | Henkel Kgaa | Sulfatierte Hydroxymischether |
DE4323252C2 (de) | 1993-07-12 | 1995-09-14 | Henkel Kgaa | Klarspüler für die maschinelle Reinigung harter Oberflächen |
DE10121724A1 (de) * | 2001-05-04 | 2002-11-07 | Cognis Deutschland Gmbh | Geminitenside |
DE10121722A1 (de) * | 2001-05-04 | 2002-11-07 | Cognis Deutschland Gmbh | Geminitenside in Klarspülmitteln |
DE10121723A1 (de) * | 2001-05-04 | 2002-11-07 | Cognis Deutschland Gmbh | Geminitenside |
DE10137925A1 (de) * | 2001-08-07 | 2003-02-20 | Cognis Deutschland Gmbh | Geminitenside und Polyethylenglycol |
DE10152142A1 (de) * | 2001-10-23 | 2003-04-30 | Cognis Deutschland Gmbh | Feste Wasch-, Spül- und Reinigungsmittel |
DE10162023A1 (de) * | 2001-12-18 | 2003-07-03 | Cognis Deutschland Gmbh | Mischungen aus Geminitensiden und Fettalkoholalkoxylaten in Klarspülmitteln |
-
2001
- 2001-05-04 DE DE10121724A patent/DE10121724A1/de not_active Withdrawn
-
2002
- 2002-04-25 EP EP02009407A patent/EP1254948B1/fr not_active Expired - Fee Related
- 2002-04-25 ES ES02009407T patent/ES2225684T3/es not_active Expired - Lifetime
- 2002-04-25 DE DE50200615T patent/DE50200615D1/de not_active Expired - Lifetime
- 2002-05-06 US US10/140,783 patent/US6794345B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0300305A2 (fr) * | 1987-07-18 | 1989-01-25 | Henkel Kommanditgesellschaft auf Aktien | Utilisation d'éthers hydroxyalkylpolyéthylenglycoliques comme produits de rinçage pour le lavage mécanique de la vaisselle |
DE19513391A1 (de) * | 1995-04-08 | 1996-10-10 | Henkel Kgaa | Bi- und multifunktionelle Mischether |
WO1998015346A1 (fr) * | 1996-10-04 | 1998-04-16 | Rhodia Inc. | Amelioration d'agents antisalissures a l'aide de tensioactifs jumeles |
EP0884298A2 (fr) * | 1997-06-12 | 1998-12-16 | Henkel Kommanditgesellschaft auf Aktien | Tensioactifs géminés, mélange de tensioactifs et compositions détergentes |
WO1999027047A1 (fr) * | 1997-11-22 | 1999-06-03 | Henkel-Ecolab Gmbh & Co. Ohg | Produit pour le nettoyage de surfaces dures |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1288281A2 (fr) * | 2001-08-07 | 2003-03-05 | Cognis Deutschland GmbH & Co. KG | Tensioactifs gémini et polyéthylène glycol |
EP1288281B1 (fr) * | 2001-08-07 | 2005-11-02 | Cognis IP Management GmbH | Tensioactifs gémini et polyéthylène glycol |
EP1306422A1 (fr) * | 2001-10-23 | 2003-05-02 | Cognis Deutschland GmbH & Co. KG | Produits solides de lavage, de rincage et de nettoyage |
EP1764408A1 (fr) | 2005-09-14 | 2007-03-21 | Cognis IP Management GmbH | Mélanges des agents tensio-actifs pour l'utilisation dans des composition de nettoyage |
WO2009100855A2 (fr) * | 2008-02-14 | 2009-08-20 | Cognis Ip Management Gmbh | Utilisation de substances tensioactives dans des nettoyants |
WO2009100855A3 (fr) * | 2008-02-14 | 2009-10-08 | Cognis Ip Management Gmbh | Utilisation de substances tensioactives dans des nettoyants |
EP2267110A3 (fr) * | 2008-02-14 | 2011-04-27 | Cognis IP Management GmbH | Utilisation de substances tensioactives dans des nettoyants |
US8148313B2 (en) | 2008-02-14 | 2012-04-03 | Cognis Ip Management Gmbh | Use of a mixture of non-ionic surfactants in cleansing compositions |
CN101945986B (zh) * | 2008-02-14 | 2012-10-10 | 考格尼斯知识产权管理有限责任公司 | 表面活性物质在清洁剂中的用途 |
Also Published As
Publication number | Publication date |
---|---|
US6794345B2 (en) | 2004-09-21 |
EP1254948B1 (fr) | 2004-07-14 |
US20030078176A1 (en) | 2003-04-24 |
DE50200615D1 (de) | 2004-08-19 |
ES2225684T3 (es) | 2005-03-16 |
DE10121724A1 (de) | 2002-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1254948B1 (fr) | Tensioactifs gemini | |
EP1254949B1 (fr) | Tensioactifs gemini pour les agents de rinçage | |
EP1254947B1 (fr) | Tensioactifs gemini | |
EP1972683B1 (fr) | Polymères amphotères en tant qu'additifs antisalissure dans des produits de lavage | |
EP1229104B1 (fr) | Produit de rinçage et de nettoyage | |
EP1229103B1 (fr) | Hydroxyéthers mixtes à haut degré d'éthoxylation | |
DE102005044028A1 (de) | Mischung oberflächenaktiver Substanzen zur Verwendung in Reinigungsmitteln | |
EP1308499B1 (fr) | Melangé tensioactif avec hydroxy-ethers mixtes et polyméres | |
EP1321511A2 (fr) | Mélanges de tensioactives geminis et alkoxylates d'alcool gras pour compositions de rincage | |
EP1321512A2 (fr) | Composition de rincage et nettoyage | |
EP1259585B1 (fr) | Agents de rincage | |
WO2002061025A1 (fr) | Hydroxy-ethers mixtes a haut degre d'ethoxylation utilises comme agents antimoussants | |
EP1250408B1 (fr) | Agents de rincage et de nettoyage | |
EP1356014B1 (fr) | Hydroxy-ethers mixtes a haut degre d'ethoxylation utilises comme agents antimoussants | |
DE10116020A1 (de) | Hydroxymischether mit hohem Ethoxylierungsgrad als Entschäumer | |
DE10003751A1 (de) | Bleichende Spül- und Reinigungsmittel | |
US20030158071A1 (en) | Rinsing and cleaning agents | |
DE19820799A1 (de) | Feste Waschmittel |
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: 20020425 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17Q | First examination report despatched |
Effective date: 20030326 |
|
AKX | Designation fees paid |
Designated state(s): BE DE ES FR GB IT |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE ES FR GB IT |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REF | Corresponds to: |
Ref document number: 50200615 Country of ref document: DE Date of ref document: 20040819 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: GERMAN |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20041008 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2225684 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050430 |
|
ET | Fr: translation filed | ||
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 |
|
26N | No opposition filed |
Effective date: 20050415 |
|
BERE | Be: lapsed |
Owner name: *COGNIS DEUTSCHLAND G.M.B.H. & CO. K.G. Effective date: 20050430 |
|
BERE | Be: lapsed |
Owner name: *COGNIS DEUTSCHLAND G.M.B.H. & CO. K.G. Effective date: 20050430 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20090514 AND 20090520 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20150522 Year of fee payment: 14 Ref country code: GB Payment date: 20150430 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20150422 Year of fee payment: 14 Ref country code: FR Payment date: 20150430 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20150630 Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 50200615 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160425 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20161230 |
|
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: 20161101 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160425 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160502 |
|
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 Effective date: 20160425 |
|
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: 20160426 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20181204 |