EP1254948B1 - Tensioactifs gemini - Google Patents

Tensioactifs gemini Download PDF

Info

Publication number
EP1254948B1
EP1254948B1 EP02009407A EP02009407A EP1254948B1 EP 1254948 B1 EP1254948 B1 EP 1254948B1 EP 02009407 A EP02009407 A EP 02009407A EP 02009407 A EP02009407 A EP 02009407A EP 1254948 B1 EP1254948 B1 EP 1254948B1
Authority
EP
European Patent Office
Prior art keywords
formula
alkyl
surfactants
cleaner
weight
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 - Fee Related
Application number
EP02009407A
Other languages
German (de)
English (en)
Other versions
EP1254948A1 (fr
Inventor
Ditmar Kischkel
Manfred Dr. Weuthen
Michael Elsner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1254948A1 publication Critical patent/EP1254948A1/fr
Application granted granted Critical
Publication of EP1254948B1 publication Critical patent/EP1254948B1/fr
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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 a 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.
  • Standard dishwashing detergents and cleaning agents are mixtures of, for example, nonionic surfactants, solubilizers, organic acids and solvents, water and, if necessary, 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 dishwashing detergent products with built-in rinse aid are being used more and more both in the home 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 washing compartment.
  • the commercial dishwashers work with only one cleaning fleet, which is only through Addition of 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 a high material compatibility, in particular with plastics. In addition, it should be easier to prepare solid cleaner 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 (I) 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 to be regarded as the collective name for polyhydric alcohols or polyalkylene glycols, ie as an organic compound which contains at least two hydroxyl groups in the mole.
  • the polyalkylene glycols are also to be understood as reaction products of polyhydric alcohols with alkoxylation reagents such as ethylene oxide and propylene oxide.
  • Hydroxyalkyl polyethylene glycol ethers are known from the prior art, for example EP 0 300 305 A2 discloses hydroxyalkyl polyethylene glycol ethers and their use in rinse aids. Those disclosed in EP 0 300 305. However, compounds contain only one hydroxyl function in the molecule.
  • WO 99/27047 A1 discloses agents for cleaning hard surfaces, the agents also containing hydroxy mixed ethers in addition to nonionic surfactants. The hydroxy mixed ethers of WO 99/27047 can have several free OH groups in the molecule, although these products are not gemini surfactants.
  • DE 195 13 391 A1 describes end group capped dimer alcohol and trimer alcohol alkoxylates and their use as foam hair surfactants.
  • EP 0 884 298 A2 relates to selected gemini surfactants whose end groups contain hydrogen carboxylate groups or sulfite groups.
  • WO 98/15346 discloses gemini surfactants which contain sulfite groups as the end group.
  • rinse aids are claimed, these agents containing surfactants according to formula I.
  • 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 having 8 to 12 Carbon atoms, especially with 10 carbon atoms.
  • gemini surfactants of the formula (I) are preferred, which are characterized in that are that they are at least 80% by weight, preferably 85 to 100% by weight, in particular 95 to Contain 100 wt.% Gemini surfactants, in which all free hydroxy groups of the polyethylene glycol 1,2-epoxyalkane units are sealed.
  • 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.
  • Dishwashing detergents 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 (II) 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 oligoglucosides.
  • 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 -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 the technical mixtures thereof, 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, p being numbers from 1 to 3 and R 1 being 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 rinsing 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 agent.
  • the detergents and cleaning agents according to the invention can contain further nonionic surfactants.
  • 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 glycides, 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 poly
  • 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 those 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.
  • monofunctional alcohols alkoxylated with 2 to 7 moles of ethylene oxide and then with 3 to 7 moles of propylene oxide, of the type already described.
  • 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-locked 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 being 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 (V) in which R 10 CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R 11 for hydrogen or methyl, R 12 for linear or branched alkyl radicals with 1 to 4 carbon atoms and w for numbers from 1 to 20 stands.
  • Typical examples are the formal insert products of on average 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 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. Reaction 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.
  • 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 with 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.
  • alkylamidoamine 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, alkyl benzene 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 sulfates, 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 ether s
  • 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 (VIII) 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 as well as their technical mixtures, which are obtained by 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 (IX) 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 capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl 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, eleyl alcohol, oleyl alcohol, eleyl alcohol, Gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl
  • 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 18 -Ph-SO 3 X (X) in which R 18 is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is 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 production is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized.
  • 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 detergents 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 composition.
  • the remainder, 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 conventional 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 of 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 powder 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 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 for example, 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 also particularly suitable. Examples of these are polymers obtainable under the name Carbopol® 940 and 941.
  • the crosslinked polyacrylates are preferably used in amounts not exceeding 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 washing and cleaning hard surfaces, preferably in the household and industrial and institutional area.
  • Hard surfaces include Ceramic surfaces, metal surfaces, painted surfaces, Plastic surfaces and surfaces made of glass, stone, concrete, porcelain and wood.
  • 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 dishwashing detergents, 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 previously listed.
  • 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 suitable for the formulation of combination products 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 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)

Claims (20)

  1. °) Agents tensioactifs géminés conformes à la formule (I) R-CHOH-CH2-[OCH2CH2]x - OCH2-CHOH-R dans laquelle R représente un reste alkyle et/ou alkényle linéraire ou ramifié ayant de 4 à 22 atomes de carbone, et x représente de 5 à 90.
  2. Agents tensioactifs géminés de formule (I) selon la revendication 1, dans laquelle x représente de 10 à 45, de préférence de 12 à 35.
  3. Agents tensioactifs géminés de formule (I) selon la revendication 1 et/ou 2, dans laquelle R représente un reste alkyle linéaire ou ramifié ayant de 8 à 12 atomes de carbone.
  4. Agents tensioactifs de formule (I) selon l'une des revendications 1 à 3 dans laquelle R représente un reste alkyle linéaire ayant de 8 à 12 atomes de carbone.
  5. Agents tensioactifs géminés de formule (I) selon l'une des revendications 1 à 4,
    caractérisés en ce qu'
    ils contiennent au moins 80 % en poids d'agents tensioactifs géminés dans lesquels tous les groupes hydroxy libres du polyéthylèneglycol sont bloqués avec des 1,2-époxyalcanes.
  6. Produits de lavage et de nettoyage contenant des agents tensioactifs géminés de formule (I) selon les revendications 1 à 5, ainsi que d'autres ingrédients usuels dans les produits de lavage et de nettoyage.
  7. Produits de lavage et de nettoyage selon la revendication 6,
    caractérisés en ce qu'
    ils renferment des agents tensioactifs géminés de formule (I), dans laquelle x représente de 5 à 90 - de préférence de 10 à 45, en particulier de 12 à 35, R représente un reste alkyle et/ou alkényle linéraire ou ramifié ayant de 4 à 22 atomes de carbone.
  8. Produits de lavage et de nettoyage selon l'une des revendications 6 à 7,
    caractérisés en ce qu'
    ils renferment des alkyl- et/ou alkénylglycosides de formule (II) R1O[G]p dans laquelle R1 représente un reste alkyle et/ou alkényle ayant de 4 à 22 atomes de carbone, G représente un reste de sucre ayant 5 ou 6 atomes de carbone, et p représente des nombres allant de 1 à 10.
  9. Produits de lavage et de nettoyage selon l'une des revendications 6 à 8,
    caractérisés en ce qu'
    ils renferment - calculé comme substance active, rapporté aux produits - de 0,01 à 25 % en poids d'agents tensioactifs géminés de formule (I).
  10. Produits de lavage et de nettoyage selon l'une des revendications 6 à9
    caractérisés en ce qu'
    ils renferment - calculé comme substance active, rapporté aux produits - de 0,01 à 30 % en poids d'alkyl- et/ou alkényloligoglycosides de formule (II).
  11. Produits de lavage et de nettoyage selon l'une des revendications 6 à 10,
    caractérisés en ce qu'
    ils renferment d'autres agents tensioactifs non ioniques, de préférence choisis dans le groupe qui est formé des alkoxylates d'alcanols, des alkoxylates d'alcanols à groupes terminaux bloqués, des esters d'alkyle inférieur d'acides gras alkoxylés et des oxydes d'amine.
  12. Produits de lavage et de nettoyage selon la revendication 11,
    caractérisés en ce qu' ils renferment - calculé comme substance active, rapporté aux produits - de 0,1 à 15 % en poids d'autres agents tensioactifs non ioniques.
  13. Produits de lavage et de nettoyage selon l'une des revendications 6 à 12,
    caractérisés en ce qu'
    ils renferment comme autres composants, des agents tensioactifs anioniques, de préférence choisis dans le groupe qui est formé d'alkyl- et/ou alkénylsulfates, d'alkyléthersulfates, d'alkylbenzènesulfonates, de monoglycéride(éther)sulfates et d'alcanesulfonates.
  14. Produits de lavage et de nettoyage selon la revendication 13,
    caractérisés en ce qu' ils renferment - calculé comme substance active, rapporté aux produits - de 0,01 à 20 % en poids d'agents tensioactifs anioniques.
  15. Produits de lavage et de nettoyage selon l'une des revendications 6 à 14 renfermant :
    a) de 0,1 à 15 % en poids - rapporté aux produits - d'agents tensioactifs qui renferment des agents tensioactifs géminés de formule (I),
    b) de 5 à 90 % en poids - rapporté aux produits - d'agents de structuration,
    c) de 0,1 à 6 % en poids - rapporté aux produits - d'enzymes de produits de nettoyage.
    d) éventuellement de 0,1 à 40 % en poids - rapporté aux produits - d'agents de blanchiment, et
    e) d'autres adjuvants et produits additifs.
  16. Utilisation d'agents tensioactifs géminés conformes à la formule (I), selon la revendication 1, en vue du lavage et du nettoyage de surfaces dures.
  17. Utilisation d'agents tensioactifs géminés de formule (I) selon la revendication 1 en vue de l'amélioration du pouvoir mouillante dans des produits de lavage et de nettoyage.
  18. Utilisation d'agents tensioactifs géminés de formule (I) selon la revendication 1, en vue de l'amélioration de la compatibilité avec les matières plastiques dans des produits de lavage et de nettoyage - en particulier dans des agents de lavage à la machine de la vaisselle qui contiennent des produits de rinçage.
  19. Utilisation d'agents tensioactifs géminés de formule (I) selon la revendication 1, pour la production simplifiée de formulations solides d'agents de nettoyage.
  20. Utilisation d'agents tensioactifs géminés de formule (I) selon la revendication 1, en tant qu'agent tensioactif antimousse dans des produits de lavage et de nettoyage.
EP02009407A 2001-05-04 2002-04-25 Tensioactifs gemini Expired - Fee Related EP1254948B1 (fr)

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 EP1254948A1 (fr) 2002-11-06
EP1254948B1 true 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)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE10121724A1 (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
US8349301B2 (en) 2002-06-04 2013-01-08 The Procter & Gamble Company Shampoo containing a gel network
US8470305B2 (en) 2002-06-04 2013-06-25 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
PL1668105T3 (pl) 2003-09-29 2019-03-29 Deb Ip Limited Kompozycje żelopodobne i pieniące o dużej zawartości alkoholu
DE102004062775A1 (de) 2004-12-21 2006-06-29 Stockhausen Gmbh Alkoholischer Pumpschaum
WO2006094387A1 (fr) 2005-03-07 2006-09-14 Deb Worldwide Healthcare Inc Compositions moussantes a haute teneur en alcool avec des agents tensioactifs a base de silicone
DE102005044028A1 (de) 2005-09-14 2007-03-15 Cognis Ip Management Gmbh Mischung oberflächenaktiver Substanzen zur Verwendung in Reinigungsmitteln
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
EP2142628B1 (fr) 2007-05-04 2018-09-12 Ecolab Inc. Procédé de nettoyer comprenant des composés au magnésium solubles à l'eau
DE102008009366A1 (de) * 2008-02-14 2009-08-20 Cognis Ip Management Gmbh Verwendung oberflächenaktiver Substanzen in Reinigungsmitteln
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

Family Cites Families (17)

* Cited by examiner, † Cited by third party
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
DE3723873A1 (de) * 1987-07-18 1989-01-26 Henkel Kgaa Verwendung von hydroxyalkylpolyethylenglykolethern in klarspuelmitteln fuer die maschinelle geschirreinigung
DE4038477A1 (de) 1990-12-03 1992-06-04 Henkel Kgaa Verfahren zur kontinuierlichen herstellung von partialglyceridsulfaten
DE4038478A1 (de) 1990-12-03 1992-06-04 Henkel Kgaa Verfahren zur 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
DE19513391A1 (de) * 1995-04-08 1996-10-10 Henkel Kgaa Bi- und multifunktionelle Mischether
US5922663A (en) * 1996-10-04 1999-07-13 Rhodia Inc. Enhancement of soil release with gemini surfactants
DE19724897A1 (de) * 1997-06-12 1998-12-17 Henkel Kgaa Tensidgemisch und Reinigungsmittel mit Gemini-Tensiden
DE19751859A1 (de) * 1997-11-22 1999-07-29 Henkel Ecolab Gmbh & Co Ohg Mittel zum Reinigen von harten Oberflächen
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
DE10121724A1 (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

Also Published As

Publication number Publication date
DE50200615D1 (de) 2004-08-19
US20030078176A1 (en) 2003-04-24
US6794345B2 (en) 2004-09-21
ES2225684T3 (es) 2005-03-16
DE10121724A1 (de) 2002-11-07
EP1254948A1 (fr) 2002-11-06

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
EP1321511A2 (fr) Mélanges de tensioactives geminis et alkoxylates d'alcool gras pour compositions de rincage
EP1308499B1 (fr) Melangé tensioactif avec hydroxy-ethers mixtes et polyméres
EP1259585B1 (fr) Agents de rincage
EP1321512A2 (fr) Composition de rincage et nettoyage
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
WO2001055289A1 (fr) Produit vaisselle et lessive a effet de blanchiment
WO1999010471A1 (fr) Detergents solides contenant des sulfates d'ester de polyglycol d'acide gras et adjuvants solides
US20030158071A1 (en) Rinsing and cleaning agents
DE19820799A1 (de) Feste Waschmittel
DE19820811A1 (de) Fließfähige Tensidzubereitungen

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