WO2002077140A1 - Produits de vaisselle manuelle - Google Patents

Produits de vaisselle manuelle Download PDF

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WO2002077140A1
WO2002077140A1 PCT/EP2002/002821 EP0202821W WO02077140A1 WO 2002077140 A1 WO2002077140 A1 WO 2002077140A1 EP 0202821 W EP0202821 W EP 0202821W WO 02077140 A1 WO02077140 A1 WO 02077140A1
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alkyl
weight
acid
hand dishwashing
radical
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PCT/EP2002/002821
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German (de)
English (en)
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Andreas Syldath
Ansgar Behler
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Cognis Deutschland Gmbh & Co. Kg
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Publication of WO2002077140A1 publication Critical patent/WO2002077140A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the invention relates to aqueous hand dishwashing detergents containing alkoxylated carboxylic acid esters and alkyl and alkenyl oligoglycosides in a specific weight ratio, and to their use in hand dishwashing detergents.
  • Liquid or concentrated surfactant solutions are used for the manual cleaning of dirty dishes, to which a whole range of very different requirements are made today. The funds should
  • Alkoxylated carboxylic acid esters are known from German Offenlegungsschrift DE-A1-19 611 999 and international application WO 94/13618, which are prepared by homogeneous catalysis in the presence of hydroxides and reducing agents or a cocatalyst. According to the two documents, such compounds can be used in washing, rinsing and cleaning agents.
  • the German Offenlegungsschrift DE-A-43 26 112 describes low-foaming general-purpose cleaners which contain alkoxylated carboxylic acid esters in a mixture with alkyl glycosides and, if appropriate, other surfactants such as alkyl sulfates, alkyl ether sulfates and fatty alcohol polyglycol ethers.
  • Such all-purpose cleaners are for cleaning hard surfaces such as clinker, Ceramic tiles, enamel, PVC or wooden floors are intended.
  • all-purpose cleaners do not have to clean surfaces with high fat and protein loads, are desired as low-foaming products which also have a lower active substance content.
  • skin mildness is much more important with hand dishwashing detergents than with all-purpose cleaners.
  • WO 00/02983 already describes hand dishwashing detergents which contain alkoxylated carboxylic acid esters in combination with anionic surfactants.
  • the present invention relates to aqueous hand dishwashing detergents
  • Alkyl and / or alkenyl oligoglucosides contain, characterized in that a and b are present in a weight ratio of 1: 3 to 3: 1.
  • the agents according to the invention can be formulated both as normal goods and as concentrates with a high active substance content, are gentle on the skin and at the same time have a voluminous foam which is stable even under high fat loads and an increased, excellent dishwashing capacity compared to conventional hand dishwashing agents.
  • Alkoxylated carboxylic acid esters which are mandatory in the agents according to the invention are known from the prior art.
  • such alkoxylated carboxylic acid esters are accessible by esterification of alkoxylated carboxylic acids with alcohols.
  • the compounds are preferably prepared by reacting carboxylic acid esters with alkylene oxides using catalysts, in particular using calcined hydrotalcite according to German Offenlegungsschrift DE-A-39 14 131, the compounds with a restricted Deliver homolome distribution.
  • Both carboxylic acid esters of monohydric alcohols and polyhydric alcohols can be alkoxylated by this process. According to the present invention, preference is given to alkoxylated carboxylic acid esters of monohydric alcohols which follow the general formula (I)
  • R 1 CO stands for an aliphatic acyl radical derived from a carboxylic acid
  • AlkO for alkylene oxide
  • R 2 for an aliphatic alkyl radical derived from a monohydric aliphatic alcohol.
  • Particularly suitable are alkoxylated carboxylic acid esters of the formula (I) in which R 1 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, AlkO for a CH2CH20, CHCH3CH2O and / or CH 2 -CHCH 3 0 radical, n on average for numbers from 3 to 20 and R 2 represents an aliphatic alkyl radical having 1 to 22 carbon atoms.
  • Preferred acyl radicals are derived from carboxylic acids having 6 to 22 carbon atoms of natural or synthetic origin, in particular from straight-chain saturated and / or unsaturated fatty acids, including technical mixtures thereof, as are obtainable by fat cleavage from animal and / or vegetable fats and oils, for example Coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, rape oil, cottonseed oil, fish oil, beef tallow and lard.
  • carboxylic acids examples include caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic, _Stea ⁇ nklare, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and / or erucic acid ,
  • alkyl radicals are derived from primary, aliphatic monofunctional alcohols having 1 to 22 carbon atoms, which can be saturated and / or unsaturated.
  • suitable monoalcohols are methanol, ethanol, propanol, butanol, pentanol and the hydrogenation products of the above-mentioned carboxylic acids with 6 to 22 carbon atoms, in particular methanol.
  • AlkO stands for the alkylene oxides which are reacted with the carboxylic acid esters and include ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide, in particular ethylene oxide alone.
  • alkO is a CH2CH2 ⁇ radical
  • n on average is a number from 5 to 15
  • R 2 is a methyl radical.
  • examples of such compounds are methyl lauric acid, methyl coconut fatty acid and methyl taig fatty acid alkoxylated with an average of 5, 7, 9 or 11 mol ethylene oxide.
  • Alkoxylated carboxylic acid esters which are formed from a mixture of C8 and C12-C18 fatty acids or fatty acid derivatives in a ratio of 30:70, reacted with 10 mol EO, are very particularly preferred.
  • R 3 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.
  • 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 index number p in the general formula (II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 3 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol as well their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 3 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above.
  • Alkyl oligoglucosides based on hydrogenated coco alcohol with a DP of 1 to 3 are preferred.
  • the agents according to the invention can contain anionic surfactants.
  • anionic surfactants are soaps, alkylbenzene sulfonates, 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 sulfate ether sulfates (monoglyme fatty acid sulfate) ) sulfates, mono- and dialkylsulfosuccinates, mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates,
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • 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 (III)
  • R 4 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, petroselachcohol, 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 fatty alcohols having 12 to 18 carbon atoms are particularly preferred.
  • ether sulfates are known anionic surfactants which are produced on an industrial scale by SO3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • CSA chlorosulfonic acid
  • ether sulfates which follow the formula (IV) are suitable
  • R 5 represents a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms
  • m represents numbers from 1 to 10
  • X represents 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, oleyl alcohol, alcohol Elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures in the form of their sodium and / or magnesium salts.
  • the ether sulfates can have both a conventional and a narrow homolog distribution.
  • ether sulfates based on adducts of on average 1 to 3 mol ethylene oxide with technical C12 / 14 or C12 / 18 coconut oil alcohol fractions in the form of their sodium and / or magnesium salts.
  • Alkane sulfonates can be divided into primary and secondary alkane sulfonates. This means compounds of the formula (V)
  • R 6 is hydrogen and R 7 is an alkyl radical with no more than 50 carbons.
  • the secondary alkanesulfonates are preferred.
  • R 6 and R 7 represent alkyl radicals, where R 6 and R 7 together should not have more than 50 carbon atoms.
  • 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 from AK Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) and FU Ahmed J.Am.Oil.Chem.Soc.
  • R 8 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.
  • monoglyceride (ether) sulfates are the reaction products monoglyceride of lauric acid, coconut fatty, palmitic acid, stearic acid monoglyceride, tallow fatty ⁇ lkla- and ethylene oxide adducts thereof with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts.
  • Monoglyceride sulfates of the formula (VI) are preferably used, in which R 8 CO stands for a linear acyl radical having 8 to 18 carbon atoms.
  • Alkylbenzenesulfonates preferably follow the formula (VII),
  • R 1 is a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms
  • Ph is a phenyl radical
  • X is 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.
  • Sulfosuccinates which are also referred to as sulfosuccinic acid esters, are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. They follow formula (VIII)
  • R 10 and R 11 are an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, a and n independently of one another are 0 or numbers from 1 to 10, where the at least a or n must be 1 and X is an alkali - Or alkaline earth metal, ammonium, alkyl ammonium, alkanol ammonium or glucammonium.
  • X is an alkali - Or alkaline earth metal, ammonium, alkyl ammonium, alkanol ammonium or glucammonium.
  • maleic acid but preferably maleic anhydride, which are esterified in the first step with optionally ethoxylated primary alcohols.
  • the mono / diester ratio can be adjusted by varying the amount of alcohol and the temperature.
  • Typical examples are sulfosuccinic acid monoesters and / or diesters in the form of their sodium salts which are derived from fatty alcohols having 8 to 18, preferably 8 to 10 or 12 to 14, carbon atoms; the fatty alcohols can be etherified with an average of 1 to 10 and preferably 1 to 5 moles of ethylene oxide and have both a conventional and preferably a narrowed homolog distribution.
  • Examples include di-n-octyl sulfosuccinate and monolauryl 3EO sulfosuccinate in the form of their sodium salts.
  • R 12 CO for a linear or branched, saturated or unsaturated acyl radical with 6 to 22 carbon atoms
  • x for numbers from 1 to 3 on average and AO for a CH2CH2O-, CH2CH (CH 3 ) 0- and / or CH (CH3) CH 0 radical
  • X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium are prepared by sulfating the corresponding fatty acid polyglycol esters. These in turn can be obtained using the relevant preparative processes in organic chemistry.
  • ethylene oxide, propylene oxide or a mixture thereof is added to the corresponding fatty acids in a random or block distribution, this reaction being acid-catalyzed, but preferably in the presence of bases such as sodium methylate or calcined hydrotalcite. If a degree of alkoxylation of 1 is desired, the intermediates can also be prepared by esterifying the fatty acids with an appropriate alkylene glycol.
  • the sulfation of the fatty acid polyglycol esters can be carried out in a manner known per se with chlorosulfonic acid or preferably gaseous sulfur trioxide, the molar ratio between fatty acid polyglycol ester and sulfating agent being in the range from 1: 0.95 to 1: 1, 2, preferably 1: 1 to 1: 1 , 1 and the reaction temperature can be 30 to 80 and preferably 50 to 60 ° C. It is also possible to undersulfate the fatty acid polyglycol esters, ie to use significantly fewer sulfating agents than would be stoichiometrically required for complete conversion.
  • molar amounts of fatty acid polyglycol ester to sulfating agent from 1: 0.5 to 1: 0.95, mixtures of fatty acid polyglycol ester sulfates and fatty acid polyglycol esters are obtained, which are also advantageous for a whole range of applications.
  • Typical examples of suitable starting materials are the addition products of 1 to 3 moles of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mole of ethylene oxide or 1 mole of propylene oxide with 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, oleolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, which are then sulfated and neutralized as described above.
  • Fatty acid polyglycol ester sulfates of the formula (IX) are preferably used in which R 12 CO for an acyl radical having 12 to 18 carbon atoms, x for an average of 1 or 2, AO for a CH2CH2 ⁇ group and X represents sodium or ammonium, such as, for example, lauric acid + 1 EO sulfate sodium salt, lauric acid + 1 EO sulfate ammonium salt,
  • Tallow fatty acid + 1 EO sulfate sodium salt tallow fatty acid + 1 EO : sulfate ammonium salt and mixtures thereof.
  • the hand dishwashing detergents according to the invention can contain further nonionic surfactants which differ from component a) and b).
  • nonionic surfactants are hydroxy mixed ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, fatty acid-N-alkyl-glucamides, protein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid ester, sugar oxides, sorbyl esters, polysorbate sorbates, sugar esters, polysorbate sorbates, sugar esters, polysorbate sorbents, sugar esters, polysorbates
  • the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • nonionic surfactants are preferably selected from the group consisting of hydroxy mixed ethers, fatty alcohol polyglycol ethers, end-capped fatty alcohol polyglycol ethers, amine oxides and fatty acid N-alkyl-glucamides.
  • HME Hydroxymischetherether—
  • R 13 represents a linear or branched alkyl radical having 2 to 18, preferably 10 to 16 carbon atoms
  • R 14 represents hydrogen or a linear or branched alkyl radical having 2 to 18 carbon atoms
  • R 15 represents hydrogen or methyl
  • R 16 represents a linear or branched, alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms
  • y represents numbers from 1 to 50, preferably 2 to 25 and in particular 5 to 15, with the proviso that the sum of the carbon atoms in the R 13 and R 14 are at least 4 and preferably 12 to 18.
  • the HME ring opening products can be either internal olefins (R 14 not equal to hydrogen) or terminal olefins (R 14 equal to hydrogen), the latter being preferred in view of the easier preparation and the more advantageous application properties.
  • the polar part of the molecule can be a poly (narrow lycol- (PE) or a polypropylene glycol chain (PP); Mixed chains of PE and PP units, whether in statistical or block distribution, are also suitable.
  • PE poly
  • PP polypropylene glycol chain
  • Typical examples are ring opening products of 1, 2-hexenepoxide, 2,3-hexenepoxide, 1,2-octene epoxide, 2,3-octene epoxide, 3,4-octene epoxide, 1,2-decene epoxide, 2,3-decene epoxide, 3,4 - Decenepoxid, 4,5-Decenepoxid, 1,2-Dodecenepoxid, 2,3-Dodecenepoxid, 3,4-Dode-Cenepoxid, 4,5-Dodecenepoxid, 5,6-Dodecenepoxid, 1, 2-Tetradecenepoxid, 2,3 -Tetradecenepoxid, 3,4- Tetradecenepoxid, 4,5-Tetradecenepoxid, 5,6-Tetradecenepoxid, 6,7-Tetradecenepoxid, 1,2-Hexadecenepoxid, 2,3-
  • R 17 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms
  • z is a number from 1 to 60, preferably 1 to 50, in particular 1 to 40.
  • the alkoxylated part of the molecule can be a polyethylene (narrowly lycol- [CH2CH2O] or a polypropylene glycol chain [CH2 (CH3) CHO]; mixed chains of PE- and PP units, be it in statistical or block distribution.
  • Fatty alcohols which are ethoxylated with 1 to 10 mol EO (ethylene oxide) are particularly preferred, as are propoxylated fatty alcohols with 1 to 10 mol PO (propylene oxide), but also mixtures of EO and PO or PO and EO.
  • the further preferred fatty alcohol polyglycol ethers are in particular adducts of 2 to 10 moles of ethylene oxide with fatty alcohols with 12 to 18 carbon atoms, adducts of 2 to 10 moles of ethylene oxide and 1 to 3 moles of propylene oxide with fatty alcohols with 12 to 18 carbon atoms.
  • Such compounds can easily be prepared by reacting the corresponding fatty alcohol polyglycol ethers of the formula (XI) with alkyl halides, preferably methyl chloride, n-butyl chloride, tert-butyl chloride in the presence of bases.
  • alkyl halides preferably methyl chloride, n-butyl chloride, tert-butyl chloride in the presence of bases.
  • Such compounds are often referred to in the literature as mixed ethers.
  • the preparation of the amine oxides of the formula (XII) starts from tertiary fatty amines which have at least one long alkyl radical and is oxidized in the presence of hydrogen peroxide.
  • R 19 represents a linear or branched alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms
  • R 20 and R 21 independently of one another are R 19 or, if appropriate hydroxy-substituted alkyl radical having 1 to 4 carbon atoms.
  • Amine oxides of the formula (XII) are preferably used, in which R 19 and R 20 are C12 / 14 or C12 / 18 coconut alkyl radicals and R 21 is a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (XII) in which R 19 is a C12 / 14 or C12 / 18 cocoalkyl radical and R 20 and R 21 are methyl or hydroxyethyl.
  • alkylamidoamine oxides of the formula (XIII), 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 C12 / 14 or C12 / 18 fatty acids with amines are formed.
  • R 24 represents a linear or branched alkenyl group having 2 to 6, preferably 2 to 4 carbon atoms and R 20 and R 21 have the meaning given in formula (XII).
  • Fatty acid N-alkyl polyhydroxyalkyiamides are nonionic surfactants which follow the formula (XIV)
  • R 31 CO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 30 for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.
  • the fatty acid N-alkylpolyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (XV):
  • the preferred fatty acid N-alkylpolyhydroxyalkylamides used are glucamides of the formula (XV) in which R 26 is an alkyl group and R 25 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures.
  • R 26 is an alkyl group
  • R 25 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, lin
  • Fatty acid N-alkylglucamides of the formula (XV) which are obtained by reductive amination of Glucose with methylamine and subsequent acylation with lauric acid or Ci2 / i4 coconut fatty acid or a corresponding derivative can be obtained.
  • the polyhydroxyalkylamides can also be derived from maltose and palatinose.
  • fatty acid N-alkylpolyhydroxyalkylamides are also the subject of a large number of publications. Their use as a thickener is known, for example, from European patent application EP 0285768 A1 (Hüls). French published patent application FR 1580491 A (Henkel) describes aqueous detergent mixtures based on sulfates and / or sulfonates, nonionic surfactants and, if appropriate, soaps, which contain fatty acid N-alkylglucamides as foam regulators. Mixtures of short- and longer-chain glucamides are described in German patent DE 4400632 C1 (Henkel).
  • German published documents DE 4326959 A1 and DE 4309567 A1 also report on the use of glucamides with longer alkyl residues than pseudoceramides in skin care products and on combinations of glucamides with protein hydrolyzates and cationic surfactants in hair care products.
  • the hand dishwashing detergents according to the invention contain amphoteric or zwitterionic surfactants.
  • amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, imidazolinium betaines and sulfobetaines.
  • Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds.
  • the starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine.
  • unsaturated carboxylic acids such as acrylic acid, is also possible.
  • betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XVI)
  • R 27 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms
  • R 28 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R 29 for alkyl radicals with 1 to 4 carbon atoms
  • u for numbers from 1 to 6
  • X for a Alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, Ci2 / i4-cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylimethylamine, stearamethyldiamethyldimethylamine, stearamdiamethyldimethylamine, stearyldimethylamethylamine, stearam.
  • carboxyalkylation products of amido amines the so-called glycinates, which follow the formula (XVII)
  • R 32 CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • q represents numbers from 1 to 3
  • R 28 , R 29 , u and X have the meanings of the formula (XVI) given above
  • Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethyl
  • R 33 represents an alkyl radical having 5 to 21 carbon atoms
  • R 34 represents a hydroxyl group
  • r represents 2 or 3.
  • These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine.
  • AEEA aminoethylethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again Ci2 / i4 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
  • the hand dishwashing detergents can contain active substances having an antimicrobial effect. Quaternized ammonium compounds, quaternized fatty acid triethanolamine ester salts (esterquats) and / or aromatic alcohols are preferably used for this purpose.
  • Suitable aromatic alcohols are special phenol derivatives, which are described in international patent publication WO 98/1524 and are commercially available under the product name Triclosan R.
  • Triclosan R As quaternized ammonium compounds, quaternized alkylamines having 6 to 22 carbon atoms in the alkyl radical s are as so-called QAC 'has long been known compounds. Compounds of the formula are suitable as esterquats +
  • R 35 CO for an acyl radical with 2 to 16 carbon atoms
  • R 36 , R 37 independently of one another for an alkyl radical having 1 to 16 carbon atoms or for a radical of
  • R 38 represents an alkyl radical with 1 to 4 carbon atoms
  • R 39 for hydrogen and / or R 35 CO and
  • X- stands for an anion
  • the quaternized carboxylic acid alkanolamine ester salts are prepared by methods which are known per se, alkanolamines of the formula (XX) being used first
  • R 36 and R 37 have the meaning given in formula (XIX), where in the case that R 36 and / or R 37 represents the rest of the formula CH2CH2OR 39 , R 39 is hydrogen, with carboxylic acids of the formula R 35 COOH esterified.
  • dimethylethanolamine methylethylethanolamine, diethylethanolamine, methylbutylethanolamine and / or methylhexylethanolamine
  • Monoalkyldiethanolamines and / or triethanolamines are preferably chosen.
  • Suitable carboxylic acids of the formula R 35 COOH are aliphatic saturated carboxylic acids such as acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, pelargonic acid, lauric acid, myristic acid, palmitic acid and their technical mixtures, such as those which occur in the pressure splitting of natural fats and oils.
  • Preferred are aliphatic saturated carboxylic acids with 8 to 12 carbon atoms, so that preferably R 35 CO stands for an aliphatic saturated acyl radical with 8 to 12 carbon atoms.
  • the use ratio of carboxylic acids to the alkanolamines is determined by the desired degree of esterification of the free hydroxyl groups of the alkanolamines. In the preferred monodiethanolamines and triethanolamines, all or only some of the free hydroxyl groups can be esterified with the carboxylic acids. If the hydroxyl group is not esterified, the general formula (XIX) R 39 represents a hydrogen. If an esterification takes place, in the general formula (XIX) R 39 stands for R 35 CO.
  • the average degree of esterification of the free hydroxyl groups in the case of the monodiethanolamines is in the range from 1.2 to 1.7 and in the case of the triethanolamines in the range from 1.5 to 1.9, ie Mjschunge ⁇ ran mono-, di- and, if necessary, the D [- or triethanolamines with carboxylic acids.
  • all free hydroxyl groups of the alkanolamines are preferably esterified with carboxylic acids.
  • XIX carboxylic acid alkanolamine ester salts of the general formula (XIX).
  • R 38 X compounds of the formula R 38 X are used, where R 38 has the meaning given in formula (XIX), R 38 preferably represents a methyl group.
  • X in the general formula (XIX) represents an anion, which preferably consists of that of methosulfate, Ethosulfate, formate, acetate, tartrate, dicarboxylate, citrate, halide, sulfate, phosphate and nitrate group is selected.
  • R 36 represents a radical of the formula CH2CH2O-OCR 35 and R 37 represents a methyl group and / or in which R 36 and R 37 represent a radical of the formula CH2CH2O are particularly preferably used as antimicrobial active substances -OCR 35 , where R 35 has the meaning given.
  • particularly suitable compounds are dimethyl-di-ethanol-ammonium-dicaprylic acid ester methosulfate, methyltriethanolammonium tricaprylic acid ester methosulfate and dimethyldiethanolammonium dipelargonic acid ester methosulfate.
  • microbiocidal active ingredients can preferably be used in amounts of 0.1 to 5% by weight, based on hand dishwashing detergent.
  • the hand dishwashing detergents according to the invention contain a) 0.1 to 30% by weight, preferably 0.5 to 25% by weight o, in particular 1 to 20% by weight, alkoxylated carboxylic acid esters, 0.1 to 30% by weight, preferably 0.5 to 25% by weight, in particular 1 to 20% by weight of alkyl and / or alkylene oligoglucosides, optionally up to 30% by weight, preferably up to 25% by weight, in particular up to 20% by weight of anionic surfactants, up to 30% by weight preferably up to 25% by weight, in particular up to 20% by weight of further nonionic surfactants, and optionally up to 20% by weight, preferably up to 10% by weight of amphoteric or zwitterionic surfactants.
  • the surfactant mixture of the hand dishwashing liquid is characterized in that the alkoxylated carboxylic acid esters and the
  • Alkyl and / or alkylene oligoglucosides are present in a weight ratio of 1: 3 to 3: 1, preferably 1: 2 to 2: 1.
  • the aqueous ones are aqueous ones.
  • Carboxylic acid esters preferably ethoxylated carboxylic acid methyl esters and
  • Alkylenoligoglucoside optionally up to 30% by weight, preferably up to 25% by weight, in particular up to 20% by weight of fatty alcohol ether sulfates, optionally up to 30% by weight, preferably up to 25% by weight, in particular up to 20% by weight of fatty alcohol polyglycol ether and up to up to 20% by weight, preferably up to 15% by weight of amphoteric or zwitterionic surfactants, preferably alkylbetaines, alkylamidobetaines, aminopropionates, imidazoliniumbetaines and sulfobetaines. It can also contain 0.5 to 90% by weight, preferably 1 to 80% by weight of water and optionally up to 10% by weight of auxiliaries and additives.
  • the percentages by weight relate to the percentage of active substance based on the composition.
  • the surfactant mixture of the hand dishwashing detergent is characterized in that the alkoxylated carboxylic acid esters and the alkyl and / or alkylene oligoglucosides are present in a weight ratio of 1: 3 to 3: 1, preferably 1: 2 to 2: 1.
  • Optional auxiliary agents such as builders, e.g. Glutaric acid, succinic acid, adipic acid, tartaric acid, gluconic acid, trisodium citrate, solvents, e.g. Acetone or ethanol, hydrotrope e.g. Cumene sulfonate, butyl glucoside, butylene glycol, viscosity regulators such as Fatty acid alkanolamides, pH regulators, e.g. Citric acid, caustic soda and potassium hydroxide, pearlescent agents such as Stearic acid derivatives. It can also contain dyes and fragrances.
  • builders e.g. Glutaric acid, succinic acid, adipic acid, tartaric acid, gluconic acid, trisodium citrate
  • solvents e.g. Acetone or ethanol
  • hydrotrope e.g. Cumene sulfonate
  • butyl glucoside butylene glycol
  • viscosity regulators such
  • fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropylate propylate propionate.
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, ⁇ -isomethyl ionone and methyl cedryl ketone
  • the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • Another object of the invention relates to the use of the alkoxylated carboxylic acid esters as a surfactant for the production of aqueous hand dishwashing detergents.
  • the mixtures can contain minor amounts of other customary auxiliaries and additives of the type already described.
  • the hand dishwashing detergents in concentrates usually have an active substance content or surfactant content - based on components (a), (b), (c) and (d) - of 10 to 45 and preferably 15 to 35% by weight and in normal goods one Active substance content from 10 to 20% by weight.
  • the determination of the dishwashing capacity was carried out with the help of the dish test [Fette, Seifen, Anstrichmitt., 74, 163 (1972)].
  • plates with a diameter of 14 cm were soiled with approx. 1.7 g ( ⁇ 2 ml) of beef tallow and stored for 24 hours at room temperature for aging.
  • the plates were then rinsed at 50 ° C. with 5 liters of tap water with a hardness of 16 ° d.
  • the hand dishwashing detergents were used at a dosage of 0.8 g active substance / l.
  • the rinsing attempt was stopped as soon as the foam blanket on the surface of the rinsing liquor no longer closes independently.
  • Formulations 1 to 4 are according to the invention, formulations V1 to V10 are used for comparison. The results are summarized in Table 1.
  • FMEO C s to 18 fatty acid + 10 EO methyl ester (weight ratio 30% by weight C8 and 70% by weight
  • APG Cl2-16-fatty alcohol-1.4-glucoside

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Abstract

L'invention concerne des produits de vaisselle manuelle aqueux contenant des esters d'acides carboxyliques alkoxylés et des oligoglycosides d'alkyle et d'alkylène dans un certain rapport massique, ainsi que l'utilisation desdits composés dans des produits de vaisselle manuelle.
PCT/EP2002/002821 2001-03-23 2002-03-14 Produits de vaisselle manuelle WO2002077140A1 (fr)

Applications Claiming Priority (2)

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DE2001114172 DE10114172A1 (de) 2001-03-23 2001-03-23 Handgeschirrspülmittel
DE10114172.6 2001-03-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11180716B2 (en) * 2017-07-28 2021-11-23 Croda, Inc. Cleaning formulation comprising a solvent additive

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4326112A1 (de) * 1993-08-04 1995-02-09 Henkel Kgaa Reinigungsmittel für harte Oberflächen
DE19830267A1 (de) * 1998-07-07 2000-01-13 Henkel Kgaa Handgeschirrspülmittel
WO2000034425A1 (fr) * 1998-12-09 2000-06-15 Cognis Deutschland Gmbh Nettoyants universels

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4326112A1 (de) * 1993-08-04 1995-02-09 Henkel Kgaa Reinigungsmittel für harte Oberflächen
DE19830267A1 (de) * 1998-07-07 2000-01-13 Henkel Kgaa Handgeschirrspülmittel
WO2000002983A1 (fr) * 1998-07-07 2000-01-20 Cognis Deutschland Gmbh Produit pour vaisselle faite a la main
WO2000034425A1 (fr) * 1998-12-09 2000-06-15 Cognis Deutschland Gmbh Nettoyants universels

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11180716B2 (en) * 2017-07-28 2021-11-23 Croda, Inc. Cleaning formulation comprising a solvent additive

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