EP1250408A2 - Rinsing and cleaning agents - Google Patents

Rinsing and cleaning agents

Info

Publication number
EP1250408A2
EP1250408A2 EP01946883A EP01946883A EP1250408A2 EP 1250408 A2 EP1250408 A2 EP 1250408A2 EP 01946883 A EP01946883 A EP 01946883A EP 01946883 A EP01946883 A EP 01946883A EP 1250408 A2 EP1250408 A2 EP 1250408A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
formula
agent according
cleaning agent
contain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01946883A
Other languages
German (de)
French (fr)
Other versions
EP1250408B1 (en
Inventor
Jörg KAHRE
Michael Elsner
Karl Heinz Schmid
Rita Köster
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.)
Cognis IP Management GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
Cognis IP Management GmbH
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Filing date
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Publication of EP1250408A2 publication Critical patent/EP1250408A2/en
Application granted granted Critical
Publication of EP1250408B1 publication Critical patent/EP1250408B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 detergents and cleaning agents containing hydroxy mixed ethers and alkyl and / or alkenyl oligoglycosides, optionally further nonionic surfactants and anionic surfactants, and the use of such mixtures in detergents and cleaning agents,
  • Means for rinsing and cleaning hard, non-textile surfaces that occur in the household and commercial sector should mostly develop a small volume of foam 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.
  • German Offenlegungsschrift DE 19738866 describes surfactant mixtures of hydroxy mixed ethers and nonionic surfactants, such as fatty alcohol polyethylene glycol / polypropylene glycol ether, optionally end-capped, which have very good foaming behavior and show excellent rinse aid effects in rinse aids.
  • the object of the present invention was to develop detergents and cleaning agents which at the same time show good foam and cleaning behavior, in particular a very good wettability of plastics and high material compatibility of the surfaces to be cleaned. Description of the invention
  • the invention relates to detergents and cleaning agents
  • R 2 represents hydrogen or a methyl or ethyl radical
  • R 3 represents hydrogen or a methyl or ethyl radical
  • R 5 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.
  • Hydroxy mixed ethers of the formula (I) are known from the literature and are described, for example, in German application DE 19738866. They are prepared by reacting 1,2-epoxyalkanes (R 4 CHOCH2), where R 4 is an aliphatic saturated, straight-chain or branched alkyl radical having 2 to 22, in particular 6 to 16 carbon atoms, with alcohols which have been alkoxylated.
  • Preferred hydroxy mixed ethers for the purposes of the invention are those derived from alkoxylates of monohydric alcohols of the formula R 1 -OH having 4 to 18 carbon atoms, where R 1 is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, stands.
  • Suitable straight-chain alcohols are butanol-1, capron, ⁇ nanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, stearyl alcohol, Nonadecanol-1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as they occur in the high-pressure hydrogenation of technical methyl esters based on fats and oils.
  • branched alcohols examples include so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are produced by the oxo process, and so-called Guerbet alcohols, which are branched in the 2-position with an alkyl group.
  • Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
  • the alcohols are used in the form of their alkoxylates, which are prepared in a known manner by reacting the alcohols in any order with ethylene oxide, propylene oxide and / or butylene oxide.
  • the rinsing and cleaning agents according to the invention absolutely contain alkyl and / or alkenyl oligoglycosides of the formula (II). They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) and J.Kahre et al. in S ⁇ FW-Journal Issue 8, 598 (1995)
  • 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 5 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, isostearyl alcohol , Nonadecanol-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 5 can be derived from primary unsaturated alcohols.
  • unsaturated alcohols are undecen-1-ol, oleyl alcohol, elaidyl alcohol, ricinol alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidone alcohol, eruca alcohol, brassidyl alcohol, palmoleyl alcohol, petroselinyl alcohol, arachyl alcohol, and their technical mixtures, which can be obtained as described above, and their technical mixtures.
  • Alkyl or alkenyl radicals R 5 which are derived from primary alcohols having 6 to 16 carbon atoms are preferred.
  • alkyl oligoglucosides of the chain length Cs-Cio which are obtained as a preliminary step in the separation of technical Cs-Ci ⁇ coconut fatty alcohol by distillation and which may be contaminated with a proportion of less than 6% by weight of Ci2 alcohol, and alkyl oligoglucosides based on technical Cg / oxoalcohols.
  • the alkyl or alkenyl radical R 5 can also be derived from primary alcohols having 12 to 14 carbon atoms.
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 2.0 are preferably used. From an application point of view, such alkyl and / or Alkenyl oligoglycosides are preferred, the degree of oligomerization of which is less than 2.0 and in particular between 1.2 and 1.7.
  • the detergents and cleaning agents according to the invention contain 0.01 to 25% by weight, preferably 0.025 to 15% by weight and in particular 0.5 to 10% by weight, of hydroxy mixed ethers of the formula (I), calculated as the active substance, based on the funds.
  • Active substance defines itself as pure substance, which is contained in the detergent and cleaning 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.
  • hydroxy mixed ethers of the formula (I) and alkyl and / or alkenyl oligoglycosides of the formula (II) in a weight ratio of 10 to 0.1 to 1 to 10, preferably 10 to 0.5 to 1 to 5, in particular 10 to use 1 to 1 to 4.
  • the agents according to the invention can contain further nonionic surfactants.
  • Typical examples of nonionic 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 glucose amides, mixed glycidyl amides, mixed acid amides, mixed acid amides, and mixed acid amides (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, and polysorbates. If the 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.
  • Fatty alcohol polyethylene glycol / polypropylene glycol ether Fatty alcohol polyethylene glycol / polypropylene glycol ether
  • fatty alcohol polyethylene glycol / polypropylene glycol ether In a preferred embodiment, fatty alcohol polyethylene glycol / polypropylene glycol ether
  • R 6 is an alkyl and / or alkenyl radical having 8 to 22 C atoms
  • R 7 is H or an alkyl radical having 1 to 8 C atoms
  • n is a number from 1 to 40, preferably 1 to 30 , in particular 1 to 15, and m represents 0 or a number from 1 to 10.
  • R 8 is an alkyl and / or alkenyl radical with 8 to 22 C atoms
  • R 9 for H or an alkyl radical with 1 to 8 C atoms
  • q for a number from 1 to 5 and r for a number of 0 to 15.
  • the 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 carbon atoms, n is a number from 1 to 10, and m for
  • Ethylene oxide with monofunctional alcohols As alcohols, the alcohols described above are like
  • Fatty alcohols, oxo alcohols and Guerbet alcohols are suitable.
  • R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms.
  • n is a number from 2 to 7
  • m is a number from 3 to 7
  • R 7 is hydrogen. It deals are addition products of 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-capped compounds of the formula (III) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n 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, n 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.
  • Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V)
  • 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 an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and technical and mixtures thereof.
  • the products are usually prepared by inserting the alkoxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotaicit. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
  • the preparation of the amine oxides of the formula (VI) starts from tertiary fatty amines which have at least one long alkyl radical and is oxidized in the presence of hydrogen peroxide.
  • R 13 represents a linear or branched alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms
  • R 14 and R 15 independently of one another are R 13 or, if appropriate hydroxy-substituted alkyl radical having 1 to 4 carbon atoms.
  • Amine oxides of the formula (VI) are preferably used in which R 13 and R 14 are C12 / 14 and C12 / i ⁇ -cocoalkyl radicals and R 15 is a methyl or a hydroxyethyl radical.
  • Amine oxides of the formula (VI) in which R 13 represents a C12 / 14 or C12 / 18 cocoalkyl radical and R 14 and R 15 have the meaning of a methyl or hydroxyethyl radical are also preferred.
  • alkylamido-amine oxides of the formula (VII), the alkylamido radical R 23 CONH being obtained by the reaction of linear or branched carboxylic acids, preferably having 6 to 22, preferably having 12 to 18, carbon atoms, in particular from 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 14 and R 15 have the meaning given in formula (VI).
  • the further nonionic surfactants can be present in the 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 can contain anionic surfactants.
  • anionic surfactants are soaps, alkyl benzene sulfonates, secondary alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerol ether sulfates, mono-ether sulfate sulfates, hydroxymischogether sulfate, fatty acid amide sulfate ethersulfate, ether amide sulfate, fatty acid amine sulfate ether sulfate, ether amide sulfate, fatty acid amine sulfate, sulfate amide, (hydroxy mixed ether sulfate), ether amide s
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Preferred anionic surfactants are 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 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 Ci6 tallow fatty alcohols or vegetable fatty alcohols of comparable carbon 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 SO3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • CSA chlorosulfonic acid
  • ether sulfates are suitable which follow the formula (IX)
  • Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 mol ethylene oxide onto capronalcohol, caprylic alcohol, 2ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol, isostyl alcohol Petselinyl 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. It is particularly preferred to use ether sulfates based on adducts of an average of 2 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.
  • Alkylbenzenesulfonates preferably follow the formula (X),
  • R 18 stands for a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph for a phenyl radical and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used.
  • Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry.
  • the usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)].
  • the new- If desired, centralized 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 A. K, 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),
  • 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.
  • 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 form of sulfuric acid with sulfuric acid trioxide.
  • monoglyceride sulfates of the formula (XI) 19 CO is a linear acyl group containing 8 in which R to 18 carbon atoms.
  • Alkane sulfonates can be divided into primary and secondary alkane sulfonates. It is understood as
  • R 20 is hydrogen and R 21 is an alkyl radical with no more than 50 carbons.
  • the secondary alkanesulfonates are preferred.
  • R 20 and R 21 represent alkyl radicals, where R 20 and R 21 together should not have more than 50 carbon atoms.
  • the washing-up and cleaning agents expediently contain 0.1 to 20% by weight, preferably 0.25 to 15% by weight, in particular 0.4 to 10% by weight, of anionic surfactants, calculated as active substance, based on the agents.
  • the rest of the detergents and cleaning agents which are missing by 100% by weight, can represent auxiliary substances and water.
  • the detergents and cleaning agents can be used both as aqueous solutions and in solid form or as
  • Gel present. It is particularly preferred that they are in the form of aqueous solutions.
  • the pH of the detergents and cleaning agents in the form of an aqueous solution is preferably in the range between 4 to 6.5, in particular between 4.5 and 6, for use as an acidic cleaner.
  • Cleaners are called the cleaners that are made by adding inorganic and organic
  • the rinsing and cleaning agents according to the invention are brought to a pH between 7 and 10, preferably between 7 and 8, by adding alkali metal hydroxide,
  • Ammonia or organic bases such as triethanolamine, adjusted.
  • auxiliaries according to the invention can be used as auxiliaries, for example solubilizers such as cumene sulfonate, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, diethylene glycol, propylene glycol monobutyl ether, polyethylene or polypropylene glycol ether with molecular weights from 600 to 1,500,000, preferably with a molecular weight from 400,000 to 800 000, or in particular contain butyl diglycol.
  • solubilizers such as cumene sulfonate, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, diethylene glycol, propylene glycol monobutyl ether, polyethylene or polypropylene glycol ether with molecular weights from 600 to 1,500,000, preferably with a molecular weight from 400,000 to 800 000, or in particular contain butyl diglycol.
  • Foam regulators such as soap, fatty acids, in particular coconut fatty acid and palm kernel fatty acid, soluble builders, such as, for example, citric acid or sodium citrate, EDTA or NTA, abrasives such as quartz or wood powder or polyethylene rubbers and thickeners such as Acrysol® can also be present.
  • soluble builders such as, for example, citric acid or sodium citrate, EDTA or NTA
  • abrasives such as quartz or wood powder or polyethylene rubbers and thickeners such as Acrysol® can also be present.
  • agents can contain cationic surfactants or biocides, for example glucoprotamine.
  • Another object of the present invention is the use of hydroxy mixed ethers in combination with alkyl and / or alkenyl oligoglycosides for rinsing and cleaning hard surfaces, preferably in the household and in the industrial and institutional fields.
  • These formulations are particularly suitable for bathroom cleaners, floor cleaners, cleaners based on the clean shower concept (e.g. bathroom cleaners, which are sprayed onto walls and fittings before and after showering so that the water and soap residues run off better, thereby eliminating the need for wiping), cockpit -Cleaner (car, plane, ship, motorcycle), window cleaner and all-purpose cleaner.
  • Hard surfaces include ceramic surfaces, metal surfaces, painted surfaces, plastic surfaces and surfaces made of glass, stone, concrete, porcelain and wood. Examples
  • the assessment of the cleaning performance of the cleaning agents on hard surfaces is based on the fact that a white dirt carrier treated with test dirt is wiped under defined conditions with a sponge soaked with the test material.
  • the test material can be used diluted or undiluted.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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  • Detergent Compositions (AREA)

Abstract

The invention relates to rinsing and cleaning agents, which comprise hydroxy mixed ethers, alkyl and/or alkenyl oligoclycosides and, optionally, further non-ionic surfactants and ionic surfactants. The invention further relates to the use of said mixtures in rinsing and cleaning agents.

Description

Spül- und ReinigungsmittelDetergent and cleaning agents
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft Spül- und Reinigungsmittel, enthaltend Hydroxymischether und Alkyl- und/oder Alkenyloligoglycoside, gegebenenfalls weitere nichtionische Tenside und anionische Tenside, sowie die Verwendung derartiger Mischungen in Spül- und Reinigungsmittel,The invention relates to detergents and cleaning agents containing hydroxy mixed ethers and alkyl and / or alkenyl oligoglycosides, optionally further nonionic surfactants and anionic surfactants, and the use of such mixtures in detergents and cleaning agents,
Stand der TechnikState of the art
Mittel für das Spülen und Reinigen harter, nichttextiler Oberflächen, die im Haushalt und Gewerbesektor vorkommen sollen meist bei Anwendung ein geringfügiges Schaumvolumen entwickeln, das sich innerhalb von wenigen Minuten signifikant weiter verringert. Mittel dieser Art sind seit langem bekannt und im Markt etabliert. Es handelt sich dabei im wesentlichen um wäßrige Tensidlösungen unterschiedlicher Art mit oder ohne Zusatz von Buildern, Lösungsvermittlern (Hydrotropen) oder Lösungsmitteln. Zum Nachweis der Wirksamkeit bei Beginn der Reinigungsarbeit wird vom Verbraucher zwar ein gewisses Schäumen der Anwendungslösung gewünscht, der Schaum soll jedoch rasch zusammenfallen, damit einmal gereinigte Flächen nicht nachgewischt werden müssen. Zu diesem Zweck werden Mittel der genannten Art üblicherweise mit schwach schäumenden nichtionischen Tensiden versetzt.Means for rinsing and cleaning hard, non-textile surfaces that occur in the household and commercial sector should mostly develop a small volume of foam 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. For this purpose, agents of the type mentioned are usually mixed with low-foaming nonionic surfactants.
In der deutschen Offenlegungschrift DE 19738866 werden Tensidmischungen aus Hydroxymischethern und nichtionischen Tensiden, wie Fettalkoholpolyethylenglycol/polypropylenglycolether, gegebenenfalls endgruppenverschlossen, beschrieben, die ein sehr gutes Schaumverhalten aufweisen und in Klarspülmitteln hervorragende Klarspüleffekte zeigen.German Offenlegungsschrift DE 19738866 describes surfactant mixtures of hydroxy mixed ethers and nonionic surfactants, such as fatty alcohol polyethylene glycol / polypropylene glycol ether, optionally end-capped, which have very good foaming behavior and show excellent rinse aid effects in rinse aids.
Aus der deutschen Offenlegungsschrift DT 2432757 ist bekannt, das Hydroxymischether als Schaumdämpfungsmittel in Wasch-, Spül- und Reinigungsmittel eingesetzt werden.From German published patent application DT 2432757 it is known that hydroxy mixed ethers can be used as foam suppressants in washing, rinsing and cleaning agents.
Aufgabe der vorliegenden Erfindung war es, Spül- und Reinigungsmittel zu entwickeln, die gleichzeitig ein gutes Schaum- und Reinigungsverhalten, insbesondere eine sehr gute Benetzungsfähigkeit von Kunststoffen und eine hohe Materialvertäglichkeit der zu reinigenden Oberflächen zeigen. Beschreibung der ErfindungThe object of the present invention was to develop detergents and cleaning agents which at the same time show good foam and cleaning behavior, in particular a very good wettability of plastics and high material compatibility of the surfaces to be cleaned. Description of the invention
Gegenstand der Erfindung sind Spül- und Reinigungsmittel enthaltendThe invention relates to detergents and cleaning agents
a. Hydroxymischether der Formel (I)a. Hydroxy mixed ethers of the formula (I)
RO[ CH2CHR20]χ[CH2CHR30]yCH2CH(OH)R4 (I) in der R1 für Alkyl- und/oder Alkenylrest mit 4 bis 22 KohlenstoffatomenRO [CH 2 CHR20] χ [CH2CHR30] y CH2CH (OH) R4 (I) in the R 1 for alkyl and / or alkenyl radical with 4 to 22 carbon atoms
R2 für Wasserstoff oder einen Methyl-, oder EthylrestR 2 represents hydrogen or a methyl or ethyl radical
R3 für Wasserstoff oder einen Methyl-, oder EthylrestR 3 represents hydrogen or a methyl or ethyl radical
R4 für einen Alkylrest mit 2 bis 22 Kohlenstoffatomen x für 0 oder 1 bis 30, y für 0 oder 1 bis 30, wobei x+y>=1 ist, steht, undR 4 is an alkyl radical having 2 to 22 carbon atoms x is 0 or 1 to 30, y is 0 or 1 to 30, where x + y> = 1, and
b. Alkyl- und/oder Alkenyloligoglykoside der Formel (II)b. Alkyl and / or alkenyl oligoglycosides of the formula (II)
R50-[G]p (II)R 5 0- [G] p (II)
in der R5 für Alkyl- und/ oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen p für eine Zahl von 1 bis 10, steht.in which R 5 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.
Hydroxymischetherhydroxy mixed
Hydroxymischether der Formel (I) sind literaturbekannt und werden beispielsweise in der deutschen Anmeldung DE 19738866 beschrieben. Sie werden hergestellt durch Umsetzung von 1 ,2-Epoxyalkanen (R4CHOCH2), wobei R4 für einen aliphatischen gesättigten, geradkettigen oder verzweigten Alkylrest mit 2 bis 22, insbesondere 6 bis 16 Kohlenstoffatomen steht, mit Alkoholen, die alkoxyliert worden sind. Bevorzugt im Sinne der Erfindung werden solche Hydroxymischether, die sich von Alkoxylaten von einwertigen Alkoholen der Formel R1-OH mit 4 bis 18 Kohlenstoffatomen ableiten, wobei R1 für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest, insbesondere mit 6 bis 16 Kohlenstoffatomen, steht. Beispiele für geeignete geradkettige Alkohole sind Butanol-1 , Capron-, Önanth-, Capryl-, Pelargon-, Caprinalkohol, Undecanol-1 , Laurylalkohol, Tridecanol-1 , Myristylalkohol, Pentadecanol-1 , Palmityl- akohol, Heptadecanol-1 , Stearylalkohol, Nonadecanol-1 , Arachidylalkohol, Heneicosanol-1 , Behenyl- alkohol sowie deren technische Mischungen, wie sie bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen anfallen. Beispiele für verzweigte Alkohole sind sogenannte Oxoalkohole, die meist 2 bis 4 Methylgruppen als Verzweigungen tragen und nach dem Oxoprozeß hergestellt werden und sogenannte Guerbetalkohole, die in 2-Stellung mit einer Alkylgruppe verzweigt sind. Geeignete Guerbetalkohole sind 2-Ethylhexanol, 2-Butyloctanol, 2-Hexyldecanol und/oder 2- Octyldodecanol.Hydroxy mixed ethers of the formula (I) are known from the literature and are described, for example, in German application DE 19738866. They are prepared by reacting 1,2-epoxyalkanes (R 4 CHOCH2), where R 4 is an aliphatic saturated, straight-chain or branched alkyl radical having 2 to 22, in particular 6 to 16 carbon atoms, with alcohols which have been alkoxylated. Preferred hydroxy mixed ethers for the purposes of the invention are those derived from alkoxylates of monohydric alcohols of the formula R 1 -OH having 4 to 18 carbon atoms, where R 1 is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, stands. Examples of suitable straight-chain alcohols are butanol-1, capron, Önanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, stearyl alcohol, Nonadecanol-1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as they occur in the high-pressure hydrogenation of technical methyl esters based on fats and oils. Examples of branched alcohols are so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are produced by the oxo process, and so-called Guerbet alcohols, which are branched in the 2-position with an alkyl group. Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
Die Alkohole werden in Form ihrer Alkoxylate eingesetzt, die durch Umsetzung der Alkohole in beliebiger Reihenfolge mit Ethylenoxid, Propylenoxid und/oder Butylenoxid auf bekannte Weise hergestellt werden.The alcohols are used in the form of their alkoxylates, which are prepared in a known manner by reacting the alcohols in any order with ethylene oxide, propylene oxide and / or butylene oxide.
Vorzugsweise werden Alkoxylate von Alkoholen, die durch Umsetzung mit 10 bis 50 Mol Ethylenoxid entstehen eingesetzt, wobei R2 und R3 für Wasserstoff steht und x+y=1-50 ist. Bevorzugt sind sowohl Alkoxylate, die durch Umsetzung von Alkohol mit 1 bis 10 Mol Propylenoxid (R2=Methyl, x=1-10) und 10 bis 30 Mol Ethylenoxid (R3=Wasserstoff, y=10-30) entstehen, und auch durch Umsetzung mit 10 bis 30 Mol Ethylenoxid (R2=Wasserstoff, x=10-30) und 1 bis 10 Mol Propylenoxid (R3=Methyl, y=1-10) entstehen.Alkoxylates of alcohols which are formed by reaction with 10 to 50 mol of ethylene oxide are preferably used, where R 2 and R 3 are hydrogen and x + y = 1-50. Both alkoxylates which are formed by reacting alcohol with 1 to 10 mol of propylene oxide (R 2 = methyl, x = 1-10) and 10 to 30 mol of ethylene oxide (R 3 = hydrogen, y = 10-30) are preferred, and also by reaction with 10 to 30 moles of ethylene oxide (R 2 = hydrogen, x = 10-30) and 1 to 10 moles of propylene oxide (R 3 = methyl, y = 1-10).
Insbesondere geeignet sind Hydroxymischether der Formel (I), wobei R2 für einen Methylrest, und R3 für Wasserstoff stehen, die vorteilhafterweise durch Umsetzung von Alkohol mit 1 bis 3 Mol Propylenoxid (x=1-3) und anschließend mit 10 bis 25 Mol Ethylenoxid (y=10— 25) hergestellt worden sind.Hydroxy mixed ethers of the formula (I) are particularly suitable, where R 2 is a methyl radical and R 3 is hydrogen, which is advantageously carried out by reacting alcohol with 1 to 3 mol of propylene oxide (x = 1-3) and then with 10 to 25 mol Ethylene oxide (y = 10-25) have been produced.
Alkyl- und/oder Alkenyloli oglykosideAlkyl and / or alkenyl oligoglycosides
Zwingend enthalten die erfindungsgemäßen Spül- und Reinigungsmittel Alkyl- und/oder Alkenyloligoglykoside der Formel (II). Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Übersichtsarbeit von Biermann et al. in Starch/Stärke 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) sowie J.Kahre et al. in SÖFW-Journal Heft 8, 598 (1995) verwiesen Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside.The rinsing and cleaning agents according to the invention absolutely contain alkyl and / or alkenyl oligoglycosides of the formula (II). They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) and J.Kahre et al. in SÖFW-Journal Issue 8, 598 (1995) 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.
Der Alkylrest R5 kann sich von primären gesättigten Alkoholen ableiten. Typische Beispiele sind Butanol-1, Capron-, Önanth-, Capryl-, Pelargon-, Caprinalkohol, Undecanol-1 , Laurylalkohol, Tridecanol-1 , Myristylalkohol, Pentadecanol-1 , Cetylalkohol, Palmitylakohol, Heptadecanol-1 , Stearyl- alkohol, Isostearylalkohol, Nonadecanol-1 , Arachidylalkohol, Heneicosanol-1 , und Behenylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxo- synthese erhalten werden.The alkyl radical R 5 can be derived from primary saturated alcohols. Typical examples are butanol-1, capron, Önanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, cetyl alcohol, palmity alcohol, heptadecanol-1, stearyl alcohol, isostearyl alcohol , Nonadecanol-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.
Der Alkenylrest R5 kann sich von primären ungesättigten Alkoholen ableiten. Typische Beispiele ungesättigter Alkohole sind Undecen-1-ol, Oleylalkohol, Elaidylalkohol, Ricinolalkohol, Linoleylalkohol, Linolenylalkohol, Gadoleylalkohol, Arachidonalkohol, Erucaalkohol, Brassidylalkohol, Palmoleylalkohol, Petroselinylalkohol, Arachylalkohol, sowie deren technische Gemische, die wie oben beschrieben erhalten werden können.The alkenyl radical R 5 can be derived from primary unsaturated alcohols. Typical examples of unsaturated alcohols are undecen-1-ol, oleyl alcohol, elaidyl alcohol, ricinol alcohol, linoleyl alcohol, linolenyl alcohol, gadoleyl alcohol, arachidone alcohol, eruca alcohol, brassidyl alcohol, palmoleyl alcohol, petroselinyl alcohol, arachyl alcohol, and their technical mixtures, which can be obtained as described above, and their technical mixtures.
Bevorzugt werden Alkyl- bzw. Alkenylrest R5, die sich von primären Alkoholen mit 6 bis 16 Kohlenstoffatomen ableiten.Alkyl or alkenyl radicals R 5 which are derived from primary alcohols having 6 to 16 carbon atoms are preferred.
Insbesondere geeignet sind Alkyloligoglucoside der Kettenlänge Cs-Cio, die als Vorlauf bei der destillativen Auftrennung von technischem Cs-Ciδ-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% Ci2-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer Cg/n-Oxoalkohole.Particularly suitable are alkyl oligoglucosides of the chain length Cs-Cio, which are obtained as a preliminary step in the separation of technical Cs-Ciδ coconut fatty alcohol by distillation and which may be contaminated with a proportion of less than 6% by weight of Ci2 alcohol, and alkyl oligoglucosides based on technical Cg / oxoalcohols.
Der Alkyl- bzw. Alkenylrest R5 kann sich ferner auch von primären Alkoholen mit 12 bis 14 Kohlenstoffatomen ableiten.The alkyl or alkenyl radical R 5 can also be derived from primary alcohols having 12 to 14 carbon atoms.
Die Indexzahl p in der allgemeinen Formel (II) gibt den Oligomerisierungsgrad (DP), d.h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier insbesondere die Werte p = 1 bis 3 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt.The index number p in the general formula (II) indicates the degree of oligomerization (DP), i.e. the distribution of mono- and oligoglycosides is present and stands for a number between 1 and 10. While p must always be an integer in a given compound and in particular can assume the values p = 1 to 3 here, the value p for a certain alkyl oligoglycoside is one analytically determined arithmetic size, which usually represents a fractional number.
Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1 ,1 bis 2,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 2,0 ist und insbesondere zwischen 1 ,2 und 1 ,7 liegt.Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 2.0 are preferably used. From an application point of view, such alkyl and / or Alkenyl oligoglycosides are preferred, the degree of oligomerization of which is less than 2.0 and in particular between 1.2 and 1.7.
In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Spül- und Reinigungsmittel 0,01 bis 25 Gew.-%, vorzugsweise 0,025 bis 15 Gew.-% und insbesondere 0,5 bis 10 Gew.-% Hydroxymischether der Formel (I) berechnet als Aktivsubstanz, bezogen auf die Mittel. Aktivsubstanz definiert sich als Reinstoff, der in dem Spül- und Reinigungsmittel enthalten ist.In a preferred embodiment, the detergents and cleaning agents according to the invention contain 0.01 to 25% by weight, preferably 0.025 to 15% by weight and in particular 0.5 to 10% by weight, of hydroxy mixed ethers of the formula (I), calculated as the active substance, based on the funds. Active substance defines itself as pure substance, which is contained in the detergent and cleaning agent.
In einer weiteren Ausführungsform enthalten die erfindungsgemäßen Spül- und Reinigungsmittel 0,01 bis 30 Gew.-%, vorzugsweise 0,1 bis 20 Gew.-% und insbesondere 0,2 bis 15 Gew.-% Alkyl- und/oder Alkenyloligoglykoside der Formel (II) berechnet als Aktivsubstanz, bezogen auf die Mittel.In a further embodiment, 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.
Weiterhin kann es bevorzugt sein, die Hydroxymischether der Formel (I) und Alkyl- und/oder Alkenyloligoglykoside der Formel (II) im Gewichtsverhältnis 10 zu 0,1 bis 1 zu 10, vorzugsweise 10 zu 0,5 bis 1 zu 5, insbesondere 10 zu 1 bis 1 zu 4 einzusetzen.It may furthermore be preferred to use the hydroxy mixed ethers of the formula (I) and alkyl and / or alkenyl oligoglycosides of the formula (II) in a weight ratio of 10 to 0.1 to 1 to 10, preferably 10 to 0.5 to 1 to 5, in particular 10 to use 1 to 1 to 4.
Nichtionische TensideNonionic surfactants
Die erfindugsgemäßen Mittel können weitere nichtionische Tenside enthalten. Typische Beispiele für nichtionische Tenside sind Alkoxylate von Alkanolen, endgruppenverschlossene Alkoxylate von Alkanolen ohne freie OH-Gruppen , alkoxylierte Fettsäureniedrigalkylester, Aminoxide, Alkylphenolpoly- glycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, Fettsäure-N-alkylglucamide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfettsäureester, Zuckerester, Sorbitanester, und Polysorbate. Sofern die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen.The agents according to the invention can contain further nonionic surfactants. Typical examples of nonionic 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 glucose amides, mixed glycidyl amides, mixed acid amides, mixed acid amides, and mixed acid amides (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, and polysorbates. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
Bevorzugt sind die weiteren nichtionische Tenside ausgewählt aus der Gruppe, die gebildet wird von Alkoxylaten von Alkanolen, insbesondere Fettalkoholpolyethylenglykol/polypropylenglykolether (FAEO/PO) der Formel (III) bzw. Fettalkoholpolypropylenglykol/polyethylenglykolether (FAPO/EO) der Formel (IV), endgruppenverschlossene Alkoxylate von Alkanole, insbesondere endgruppenverschlossene Fettalkoholpolyethylenglykol/polypropylenglykolether bzw. endgruppenverschlossene Fett- alkoholpolypropylenglykol/polyethylenglykolether, und Fettsäureniedrigalkylester und Aminoxiden. Fettalkoholpolyethylenglykol/polypropylenglykoletherThe 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. Fatty alcohol polyethylene glycol / polypropylene
In einer bevorzugten Ausführungsform werden Fettalkoholpolyethylenglykol/polypropylenglykolether derIn a preferred embodiment, fatty alcohol polyethylene glycol / polypropylene glycol ether
Formel (III), die gegebenenfalls endgruppenverschlossen sind,Formula (III), which are optionally end group-closed,
R60(CH2CH20)n[CH2(CH3)CHO]mR7 (III)R 6 0 (CH 2 CH 2 0) n [CH2 (CH3) CHO] m R 7 (III)
eingesetzt, in der R6 für einen Alkyl- und/oder Alkenylrest mit 8 bis 22 C-Atomen, R7 für H oder einen Alkylrest mit 1 bis 8 C-Atomen, n für eine Zahl von 1 bis 40, vorzugsweise 1 bis 30, insbesondere 1 bis 15, und m für 0 oder eine Zahl von 1 bis 10 steht.used, in which R 6 is an alkyl and / or alkenyl radical having 8 to 22 C atoms, R 7 is H or an alkyl radical having 1 to 8 C atoms, n is a number from 1 to 40, preferably 1 to 30 , in particular 1 to 15, and m represents 0 or a number from 1 to 10.
Fettalkoholpolypropylenglykol/polyethylenglykoletherFatty alcohol polypropylene glycol / polyethylene
Ebenso geeignet sind Fettalkoholpolypropylenglykol/polyethylenglykolether der Formel (IV), die gegebenenfalls endgruppenverschlossen sind,Also suitable are fatty alcohol polypropylene glycol / polyethylene glycol ethers of the formula (IV), which are optionally end-capped,
R80[CH2(CH3)CHO]q(CH2CH2θ)rR9 (IV)R80 [CH2 (CH3) CHO] q (CH 2 CH2θ) rR 9 (IV)
in der R8 für einen Alkyl- und/oder Alkenylrest mit 8 bis 22 C-Atomen, R9 für H oder einen Alkylrest mit 1 bis 8 C-Atomen, q für eine Zahl von 1 bis 5 und r für eine Zahl von 0 bis 15 steht.in which R 8 is an alkyl and / or alkenyl radical with 8 to 22 C atoms, R 9 for H or an alkyl radical with 1 to 8 C atoms, q for a number from 1 to 5 and r for a number of 0 to 15.
Einer bevorzugten Ausführungsform entsprechend enthalten die erfindungsgemäßen Mittel Fettalkohol- polyethylenglykol/polypropylenglykolether der Formel (III), in der R6 für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest mit 8 bis 16 C-Atomen, n für eine Zahl von 1 bis 10, und m fürAccording to a preferred embodiment, the 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 carbon atoms, n is a number from 1 to 10, and m for
0 und R7 für Wasserstoff steht. Es handelt sich hierbei um Anlagerungsprodukte von 1 bis 10 Mol0 and R 7 represents hydrogen. These are addition products of 1 to 10 moles
Ethylenoxid an monofunktionelle Alkohole. Als Alkohole sind die oben beschriebenen Alkohole wieEthylene oxide with monofunctional alcohols. As alcohols, the alcohols described above are like
Fettalkohole, Oxoalkohole und Guerbetalkohole geeignet.Fatty alcohols, oxo alcohols and Guerbet alcohols are suitable.
Auch geeignet sind von solchen Alkoholethoxylaten solche, die eine eingeengte Homologenverteilung aufweisen.Of such alcohol ethoxylates, those are also suitable which have a narrow homolog distribution.
Weitere geeignete Vertreter von nichtendgruppenverschlossenen Vertretern sind solche der Formel (III), in der R6 für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest mit 8 bis 16 C-Other suitable representatives of non-end-capped representatives 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.
Atomen, n für eine Zahl von 2 bis 7, m für eine Zahl von 3 bis 7 und R7 für Wasserstoff steht. Es handelt sich hierbei um Anlagerungsprodukte von zunächst mit 2 bis 7 Mol Ethylenoxid und dann mit 3 bis 7 Mol Propylenoxid alkoxylierten monofunktionellen Alkohole der schon beschriebenen Art.Atoms, n is a number from 2 to 7, m is a number from 3 to 7 and R 7 is hydrogen. It deals are addition products of 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.
Die endgruppenverschlossenen Verbindungen der Formel (III) sind mit einer Alkylgruppe mit 1 bis 8 C- Atomen verschlossen (R7). Häufig werden derartige Verbindungen in der Literatur auch als Mischether bezeichnet. Geeignete Vertreter sind Methylgruppenverschlossene Verbindungen der Formel (III), in denen R6 für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest mit 8 bis 16 C- Atomen, n für eine Zahl von 2 bis 7, m für eine Zahl von 3 bis 7 und R7 für eine Methylgruppe steht. Derartige Verbindungen können leicht durch Umsetzung der entsprechenden nicht endgruppenverschlossenen Fettalkoholpolyethylenglykol/polypropylenglykolether mit Methylchlorid in Gegenwart einer Base hergestellt werden,The end group-capped compounds of the formula (III) are capped with an alkyl group having 1 to 8 carbon atoms (R 7 ). Such compounds are often referred to in the literature as mixed ethers. Suitable representatives are methyl-capped compounds of the formula (III) in which R 6 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n 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,
Geeignete Vertreter von Alkylgruppenverschlossenen Verbindungen sind solche der Formel (III), in denen R6 für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest mit 8 bis 16 C- Atomen, n für eine Zahl von 5 bis 15, m für 0 und R7 für eine Alkylgruppe mit 4 bis 8 C-Atomen steht. Bevorzugt wird der Endgruppenverschluß mit einer geradkettigen oder verzweigten Butylgruppe durchgeführt, indem der entsprechende Fettalkoholpolyethylenglykolether mit n-Butylchlorid oder mit tert. Butylchlorid in Gegenwart von Basen umgesetzt wird.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, n 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.
Anstelle der Verbindungen der Formel (III) oder in Mischung mit ihnen können gegebenenfalls endgruppenverschlossene Fettalkoholpolypropylenglykol/polyethylenglykolether der Formel (IV) enthalten sein. Derartige Verbindungen werden beispielsweise in der deutschen Offenlegungsschrift DE-A1- 43 23 252 beschrieben. Besonders bevorzugte Vertreter der Verbindungen der Formel (IV) sind solche, in denen R8 für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest mit 8 bis 16 C-Atomen, q für eine Zahl von 1 bis 5, r für eine Zahl von 1 bis 6 und R9 für Wasserstoff steht. Es handelt sich hierbei vorzugsweise um Anlagerungsprodukte von 1 bis 5 Mol Propylenoxid und von 1 bis 6 Mol Ethylenoxid an monofunktionelle Alkohole, die bereits im Zusammenhang mit den Hydroxymischethem als geeignet beschrieben worden sind. Alkoxylierte FettsäureniedrigalkylesterInstead of the compounds of the formula (III) or in a mixture with them, 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. 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 hydroxy mixed ethers. Alkoxylated fatty acid lower alkyl esters
Als alkoxylierte Fettsäureniedrigalkylester kommen Tenside der Formel (V) in Betracht,Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V)
R10CO-(OCH2CHR«)WOR12 (V)R10CO- (OCH 2 CHR «) W OR12 (V)
in der R10CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R11 für Wasserstoff oder Methyl, R12 für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und w für Zahlen von 1 bis 20 steht. Typische Beispiele sind die formalen Einschubprodukte von durchschnittlich 1 bis 20 und vorzugsweise 5 bis 10 Mol Ethylen- und/oder Propylenoxid in die Methyl-, Ethyl-, Propyl-, Isopropyl-, Butyl- und tert.-Butylester von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen. Üblicherweise erfolgt die Herstellung der Produkte durch Insertion der Alkoxide in die Carbonylesterbindung in Gegenwart spezieller Katalysatoren, wie z.B. calcinierter Hydrotaicit. Besonders bevorzugt sind Umsetzungsprodukte von durchschnittlich 5 bis 10 Mol Ethylenoxid in die Esterbindung von technischen Kokosfettsäuremethylestern.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 an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and technical and mixtures thereof. The products are usually prepared by inserting the alkoxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotaicit. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
Aminoxideamine oxides
Als Aminoxide können Verbindungen der Formel (VI) und/oder eingesetzt werden.Compounds of the formula (VI) and / or can be used as amine oxides.
R15R15
R«-N->0 (VI)R «-N-> 0 (VI)
I 14I 14
(VII) (VII)
Bei der Herstellung der Aminoxide der Formel (VI) geht man von tertiären Fettaminen aus, die mindestens einen langen Alkylrest aufweisen, und oxidiert sie in Gegenwart von Wasserstoffperoxid. Bei den im Sinne der Erfindung in Betracht kommenden Aminoxiden der Formel (VI), steht R13 für einen linearen oder verzweigten Alkylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, sowie R14 und R15 unabhängig voneinander für R13 oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen. Vorzugsweise werden Aminoxide der Formel (VI) eingesetzt, in der R13 und R14 für C12/14- bzw. Ci2/iδ-Kokosalkylreste stehen und R15 einen Methyl- oder einen Hydroxyethylrest bedeutet. Ebenfalls bevorzugt sind Aminoxide der Formel (VI), in denen R13 für einen C12/14- bzw. C12/18- Kokosalkylrest steht und R14 und R15 die Bedeutung eines Methyl- oder Hydroxyethylrestes haben. Weitere geeignete Aminoxide sind Alkylamido-aminoxide der Formel (VII), wobei der Alkylamido-Rest R23CONH durch die Reaktion von linearen oder verzweigten Carbonsäuren, vorzugsweise mit 6 bis 22, bevorzugt mit 12 bis 18 Kohlenstoffatomen, insbesondere aus C12/14- bzw. C12/18- Fettsäuren mit Aminen entsteht. Dabei stellt R24 eine linerare oder verzweigte Alkenylgruppe dar mit 2 bis 6, vorzugsweise 2 bis 4 Kohlenstoffatomen und R14 und R15 haben die in Formel (VI) angegebene Bedeutung.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. In the case of the amine oxides of the formula (VI) which are suitable for the purposes of the invention, R 13 represents a linear or branched alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms, and R 14 and R 15 independently of one another are R 13 or, if appropriate hydroxy-substituted alkyl radical having 1 to 4 carbon atoms. Amine oxides of the formula (VI) are preferably used in which R 13 and R 14 are C12 / 14 and C12 / iδ-cocoalkyl radicals and R 15 is a methyl or a hydroxyethyl radical. Amine oxides of the formula (VI) in which R 13 represents a C12 / 14 or C12 / 18 cocoalkyl radical and R 14 and R 15 have the meaning of a methyl or hydroxyethyl radical are also preferred. Further suitable amine oxides are alkylamido-amine oxides of the formula (VII), the alkylamido radical R 23 CONH being obtained by the reaction of linear or branched carboxylic acids, preferably having 6 to 22, preferably having 12 to 18, carbon atoms, in particular from 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 14 and R 15 have the meaning given in formula (VI).
Die weiteren nichtionische Tenside können in den erfindungsgemäßen Mitteln in Mengen von 0,1 bis 15 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, insbesondere 1 bis 8 Gew.-% enthalten sein, berechnet als Aktivsubstanz, bezogen auf die Mittel.The further nonionic surfactants can be present in the 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.
Gemäß der vorliegenden Erfindung können die Spül- und Reinigungsmittel anionische Tenside enthalten.According to the present invention, the rinsing and cleaning agents can contain anionic surfactants.
Anionische TensideAnionic surfactants
Typische Beispiele für anionische Tenside sind Seifen, Alkylbenzolsulfonate, sekundäre Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersulfonate, -Methylestersulfonate, Sulfofettsäuren, Alkyl- und/oder Alkenylsulfate, Alkylethersulfate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglycerid(ether)sulfate, Fettsäureamid(ether)sulfate, Mono- und Dialkylsulfosuccinate, Mono- und Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbonsäuren und deren Salze, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, N-Acylaminosäuren wie beispielsweise Acyllactylate, Acyltartrate, Acylglutamate und Acylaspartate, Alkyloligoglucosidsulfate, Proteinfettsäurekondensate (insbesondere pflanzliche Produkte auf Weizenbasis) und Alkyl(ether)phosphate. Sofern die anionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen. Vorzugsweise sind als anionische Tenside Alkyl- und/oder Alkenylsulfate, Alkylethersulfate, Alkylbenzolsulfonate, Monoglycerid(ether)sulfate und Alkansulfonate, insbesondere Fettalkoholsulfate, Fettalkoholethersulfate, sekundäre Alkansulfonate und lineare Alkylbenzolsulfonate.Typical examples of anionic surfactants are soaps, alkyl benzene sulfonates, secondary alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerol ether sulfates, mono-ether sulfate sulfates, hydroxymischogether sulfate, fatty acid amide sulfate ethersulfate, ether amide sulfate, fatty acid amine sulfate ether sulfate, ether amide sulfate, fatty acid amine sulfate, sulfate amide, (hydroxy mixed ether sulfate), ether amide sulfate, fatty acid amide sulfate, fatty acid amide sulfate, fatty acid amide sulfate, fatty acid amide sulfate, fatty acid amide sulfate, hydroxymic ether sulfate, sulfate, (methyl ether sulfate), sulfate, (methyl ether sulfate) sulfate, fatty acid amide sulfate, fatty acid amide sulfate amate sulfate, hydroxymic ether sulfate, sulfate, (methyl mixed sulfate etherate), fatty acid, and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as, for example, acyl lactylates, acyl tartrate and acyl glucate glucosate products (acyl glucate glucosate products), ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Preferred anionic surfactants are 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- und/oder AlkenylsulfateAlkyl and / or alkenyl sulfates
Unter Alkyl- und/oder Alkenylsulfaten, die auch häufig als Fettalkoholsulfate bezeichnet werden, sind die Sulfatierungsprodukte primärer Alkohole zu verstehen, die der Formel (VIII) folgen,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 60-S03X (VIII)R 6 0-S0 3 X (VIII)
in der R16 für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht.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.
Typische Beispiele für Alkylsulfate, die im Sinne der Erfindung Anwendung finden können, sind die Sulfatierungsprodukte von Capronalkohol, Caprylalkohol, Caprinalkohol, 2-Ethylhexylalkohol, Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol sowie deren technischen Gemischen, die durch Hochdruckhydrierung technischer Methylesterfraktionen oder Aldehyden aus der Roelenschen Oxosynthese erhalten werden. Die Sulfatierungsprodukte können vorzugsweise in Form ihrer Alkalisalze und insbesondere ihrer Natriumsalze eingesetzt werden. Besonders bevorzugt sind Alkylsulfate auf Basis von Ci6 -Talgfettal- koholen bzw. pflanzliche Fettalkohole vergleichbarer C-Kettenverteilung in Form ihrer Natriumsalze.Typical examples of 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 Ci6 tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts are particularly preferred.
Alkylethersulfatealkyl ether
Alkylethersulfate ("Ethersulfate") stellen bekannte anionische Tenside dar, die großtechnisch durch SO3- oder Chlorsulfonsäure (CSA)-Sulfatierung von Fettalkohol- oder Oxoalkoholpolyglycolethem und nachfolgende Neutralisation hergestellt werden. Im Sinne der Erfindung kommen Ethersulfate in Betracht, die der Formel (IX) folgen,Alkyl ether sulfates ("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. For the purposes of the invention, ether sulfates are suitable which follow the formula (IX)
Ri70-(CH2CH2θ)aS03X (IX) in der R17 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, a für Zahlen von 1 bis 10 und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammo- nium, Alkanolammonium oder Glucammonium steht. Typische Beispiele sind die Sulfate von Anlagerungsprodukten von durchschnittlich 1 bis 10 und insbesondere 2 bis 5 Mol Ethylenoxid an Capronal- kohol, Caprylalkohol, 2Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalko- hol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Pe- troselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen in Form ihrer Natrium- und/oder Magnesiumsalze. Die Ethersulfate können dabei sowohl eine konventionelle als auch eine eingeengte Homologenverteilung aufweisen. Besonders bevorzugt ist der Einsatz von Ethersulfaten auf Basis von Addukten von durchschnittlich 2 bis 3 Mol Ethylenoxid an technische C12/14- bzw. C12/18- Kokosfettalkoholfraktionen in Form ihrer Natrium- und/oder Magnesiumsalze.Ri 7 0- (CH 2 CH2θ) a S0 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 mol ethylene oxide onto capronalcohol, caprylic alcohol, 2ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, oleyl alcohol, isostyl alcohol, isostyl alcohol Petselinyl 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. It is particularly preferred to use ether sulfates based on adducts of an average of 2 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.
Alkylbenzolsulfonatealkylbenzenesulfonates
Alkylbenzolsulfonate folgen vorzugsweise der Formel (X),Alkylbenzenesulfonates preferably follow the formula (X),
R18-Ph-S03X (X)R 18 -Ph-S0 3 X (X)
in der R18 für einen verzweigten, vorzugsweise jedoch linearen Alkylrest mit 10 bis 18 Kohlenstoffatomen, Ph für einen Phenylrest und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylam- monium, Alkanolammonium oder Glucammonium steht. Vorzugsweise werden Dodecylbenzolsulfonate, Tetradecylbenzolsulfonate, Hexadecylbenzolsulfonate sowie deren technische Gemische in Form der Natriumsalze eingesetzt.in which R 18 stands for a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph for a phenyl radical and X for 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.
Monoqlvcerid(ether)sulfateMonoqlvcerid (ether) sulfates
Monoglyceridsulfate und Monoglyceridethersulfate stellen bekannte anionische Tenside dar, die nach den einschlägigen Methoden der präparativen organischen Chemie erhalten werden können. Üblicherweise geht man zu ihrer Herstellung von Triglyceriden aus, die gegebenenfalls nach Ethoxylierung zu den Monoglyceriden umgeestert und nachfolgend sulfatiert und neutralisiert werden. Gleichfalls ist es möglich, die Partialglyceride mit geeigneten Sulfatierungsmitteln, vorzugsweise gasförmiges Schwefeltrioxid oder Chlorsulfonsäure umzusetzen [vgl. EP 0561825 B1, EP 0561999 B1 (Henkel)]. Die neu- tralisierten Stoffe können - falls gewünscht - einer Ultrafiltration unterworfen werden, um den Elektrolytgehalt auf ein gewünschtes Maß zu vermindern [DE 4204700 A1 (Henkel)]. Übersichten zur Chemie der Monoglyceridsulfate sind beispielsweise von A. K, Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) und F. U. Ahmed J.Am.Oil.Chem.Soc. 67, 8 (1990) erschienen. Die im Sinne der Erfindung einzusetzenden Monoglycerid(ether)sulfate folgen der Formel (XI), 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 new- If desired, centralized 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 A. K, 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),
II
CH-0(CH2CH20)dH (XI)CH-0 (CH 2 CH 2 0) dH (XI)
I I
in der R19CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, c, d und e in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäure- monoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze.' Vorzugsweise werden Monoglyceridsulfate der Formel (XI) eingesetzt, in der R19CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht.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 form of sulfuric acid with sulfuric acid trioxide. 'Preferably, monoglyceride sulfates of the formula (XI), 19 CO is a linear acyl group containing 8 in which R to 18 carbon atoms.
Alkansulfonatealkanesulfonates
Alkansulfonate lassen sich in primäre und sekundäre Alkansulfonate einteilen. Darunter versteht manAlkane sulfonates can be divided into primary and secondary alkane sulfonates. It is understood as
Verbindungen der Formel (XII),Compounds of the formula (XII),
wobei bei primären Alkanosulfonaten R20 für Wasserstoff und R21 für einen Alkylrest mit nicht mehr als 50 Kohlenstoffen steht. Bevorzugt sind die sekundären Alkansulfonate.where in primary alkanosulfonates R 20 is hydrogen and R 21 is an alkyl radical with no more than 50 carbons. The secondary alkanesulfonates are preferred.
R20 und R21 stehen für Alkylreste, wobei R20 und R21 zusammen nicht mehr als 50 Kohlenstoffatome haben sollen.R 20 and R 21 represent alkyl radicals, where R 20 and R 21 together should not have more than 50 carbon atoms.
Zweckmäßigerweise enthalten die Spül- und Reinigungsmittel 0,1 bis 20 Gew.-%, vorzugsweise 0,25 bis 15 Gew.-%, insbesondere 0,4 bis 10 Gew.-% anionische Tenside, berechnet als Aktivsubstanz, bezogen auf die Mittel. Den zu 100 Gew.-% fehlenden Rest der Spül- und Reinigungsmittel können Hilfsstoffe sowie Wasser darstellen. Die Spül- und Reinigungsmittel können sowohl als wässrige Lösungen, als auch in fester Form oder alsThe washing-up and cleaning agents expediently contain 0.1 to 20% by weight, preferably 0.25 to 15% by weight, in particular 0.4 to 10% by weight, of anionic surfactants, calculated as active substance, based on the agents. The rest of the detergents and cleaning agents, which are missing by 100% by weight, can represent auxiliary substances and water. The detergents and cleaning agents can be used both as aqueous solutions and in solid form or as
Gel vorliegen. Insbesondere bevorzugt ist, daß sie in Form von wäßrigen Lösungen vorliegen.Gel present. It is particularly preferred that they are in the form of aqueous solutions.
Der pH-Wert der Spül- und Reinigungsmittel in Form von wäßrigen Lösung liegt bevorzugt im Bereich zwischen 4 bis 6,5, insbesondere zwischen 4,5 bis 6 für die Anwendung als saurer Reiniger. Als saureThe pH of the detergents and cleaning agents in the form of an aqueous solution is preferably in the range between 4 to 6.5, in particular between 4.5 and 6, for use as an acidic cleaner. As sour
Reiniger werden die Reiniger bezeichnet, die durch Zusatz von anorganischen und organischenCleaners are called the cleaners that are made by adding inorganic and organic
Säuren, insbesondere Citronensäure und Essigsäure und deren Salzen, wie zum Beispiel Tri- natriumcitrat auf einen pH-Wert <= 6,5 eingestellt werden,Acids, in particular citric acid and acetic acid and their salts, such as, for example, trisodium citrate, are adjusted to a pH <= 6.5,
Um als alkalische Reiniger zu wirken werden die erfindungsgemäßen Spül- und Reinigungsmittel auf einen pH-Werten zwischen 7 bis 10, vorzugsweise zwischen 7 bis 8, durch Zusatz von Alkalihydroxid,In order to act as an alkaline cleaner, the rinsing and cleaning agents according to the invention are brought to a pH between 7 and 10, preferably between 7 and 8, by adding alkali metal hydroxide,
Ammoniak, oder organischen Basen wie zum Beispiel Triethanolamin, eingestellt.Ammonia, or organic bases such as triethanolamine, adjusted.
Die erfindungsgemäßen Mittel können als Hilfsstoffe beispielsweise Lösungsvermittler wie Cumol- sulfonat, Ethanol, Isopropylalkohol, Ethylenglycol, Propylenglycol, Butylglycol, Diethylenglycol, Propylenglycolmonobutylether, Polyethylen- bzw. polypropylenglycolether mit Molmassen von 600 bis 1 500 000, vorzugsweise mit einer Molmasse von 400 000 bis 800 000, oder insbesondere Butyldiglycol enthalten. Weiterhin können Schaumregulatoren, wie beispielsweise Seife, Fettsäuren, insbesondere Kokosfettsäure und Palmkernfettsäure, lösliche Builder, wie beispielsweise Citronensäure bzw. Natriumeitrat, EDTA oder NTA, Abrasivstoffe, wie Quarz- bzw. Holzmehl oder Polyethylenreibkörper und Verdicker wie Acrysol® enthalten sein.The auxiliaries according to the invention can be used as auxiliaries, for example solubilizers such as cumene sulfonate, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, diethylene glycol, propylene glycol monobutyl ether, polyethylene or polypropylene glycol ether with molecular weights from 600 to 1,500,000, preferably with a molecular weight from 400,000 to 800 000, or in particular contain butyl diglycol. Foam regulators, such as soap, fatty acids, in particular coconut fatty acid and palm kernel fatty acid, soluble builders, such as, for example, citric acid or sodium citrate, EDTA or NTA, abrasives such as quartz or wood powder or polyethylene rubbers and thickeners such as Acrysol® can also be present.
In vielen Fällen ist eine zusätzliche bakterizide Wirkung erwünscht, weswegen die Mittel kationische Tenside oder Biozide, beispielsweise Glucoprotamin, enthalten können.In many cases an additional bactericidal action is desired, which is why the agents can contain cationic surfactants or biocides, for example glucoprotamine.
Ein weiteren Gegenstand der vorliegenden Erfindung ist die Verwendung von Hydroxymischethern in Kombination mit Alkyl- und/oder Alkenyloligoglykoside zum Spülen und Reinigen von harten Oberflächen, vorzugsweise im Haushalt und den industriellen- und institutionellen Bereich. Besonders geeignet zeigen sich diese Rezepturen für Badezimmerreiniger, Fußbodenreiniger, Reiniger nach dem clean shower Konzept (z.B. Badezimmerreiniger, der vor und nach dem Duschen auf Wände und Armaturen aufgesprüht wird, damit das Wasser und Seifenreste besser ablaufen, und dadurch ein Nachwischen entfällt), Cockpit-Reiniger (Auto, Flugzeug, Schiff, Motorrad), Fensterreiniger und Allzweckreiniger. Harte Oberflächen sind u.a. Keramikflächen, Metallflächen, lackierte Flächen, Kunststoffoberflächen und Oberflächen aus Glas, Stein, Beton, Porzellan und Holz. BeispieleAnother object of the present invention is the use of hydroxy mixed ethers in combination with alkyl and / or alkenyl oligoglycosides for rinsing and cleaning hard surfaces, preferably in the household and in the industrial and institutional fields. These formulations are particularly suitable for bathroom cleaners, floor cleaners, cleaners based on the clean shower concept (e.g. bathroom cleaners, which are sprayed onto walls and fittings before and after showering so that the water and soap residues run off better, thereby eliminating the need for wiping), cockpit -Cleaner (car, plane, ship, motorcycle), window cleaner and all-purpose cleaner. Hard surfaces include ceramic surfaces, metal surfaces, painted surfaces, plastic surfaces and surfaces made of glass, stone, concrete, porcelain and wood. Examples
Anwendungstechnische Untersuchungen. Die Beurteilung der Reinigungsleistung der Reinigungsmittel auf harten Oberflächen beruht darauf, daß ein mit Testschmutz behandelter weißer Schmutzträger unter definierten Bedingungen mit einem mit dem Prüfgut getränkten Schwamm gewischt wird. Das Prüfgut kann verdünnt oder unverdünnt eingesetzt werden. Der Reinigungseffekt wird fotoelektrisch gegen den unbehandelten weißen Schmutzträger (=100%) gemessen (Qualitätsnormen für Fußbodenpflege- und Reinigungsmittel, Wischpflegemittel in Seifen - Öle - Fette - Wachse - 112, 10 (1986)).Application studies. The assessment of the cleaning performance of the cleaning agents on hard surfaces is based on the fact that a white dirt carrier treated with test dirt is wiped under defined conditions with a sponge soaked with the test material. The test material can be used diluted or undiluted. The cleaning effect is measured photoelectrically against the untreated white dirt carrier (= 100%) (quality standards for floor care and cleaning agents, wiping agents in soaps - oils - fats - waxes - 112, 10 (1986)).
In der folgenden Tabelle sind die Vergleichsbeispiele (V) den erfindungsgemäßen Beispielen (E) gegenübergestellt. The following table compares the comparative examples (V) with the examples (E) according to the invention.

Claims

Patentansprüche claims
1. Spül- und Reinigungsmittel enthaltend1. Containing detergents and cleaning agents
a, Hydroxymischether der Formel (I)a, hydroxy mixed ethers of the formula (I)
R 0[ CH2CH(R2)0]χ[CH2CH(R3)0]yCH2CH(OH)R4 (I) in der R1 für Alkyl- und/oder Alkenylrest mit 4 bis 22 KohlenstoffatomenR 0 [CH 2 CH (R2) 0] χ [CH 2 CH (R3) 0] yCH2CH (OH) R4 (I) in the R 1 for alkyl and / or alkenyl radical having 4 to 22 carbon atoms
R2 für Wasserstoff oder einen Methyl-, oder EthylrestR 2 represents hydrogen or a methyl or ethyl radical
R3 für Wasserstoff oder einen Methyl-, oder EthylrestR 3 represents hydrogen or a methyl or ethyl radical
R4 für einen Alkylrest mit 2 bis 22 Kohlenstoffatomen x für 0 oder 1 bis 30, y für 0 oder 1 bis 30, wobei x+y>=1 ist, steht,R 4 is an alkyl radical with 2 to 22 carbon atoms x is 0 or 1 to 30, y is 0 or 1 to 30, where x + y> = 1,
b. Alkyl- und/oder Alkenyloligoglykoside der Formel (II)b. Alkyl and / or alkenyl oligoglycosides of the formula (II)
R50-[G]p (II)R 5 0- [G] p (II)
in der R5 für Alkyl- und/ oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen p für eine Zahl von 1 bis 10, steht.in which R 5 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.
2. Spül- und Reinigungsmittel nach Anspruch 1 , dadurch gekennzeichnet, dass sie Hydroxymischether der Formel (I) enthalten in der R1 für einen Alkylrest mit 4 bis 18 Kohlenstoffatomen steht.2. Detergent and cleaning agent according to claim 1, characterized in that they contain hydroxy mixed ethers of the formula (I) in which R 1 represents an alkyl radical having 4 to 18 carbon atoms.
3. Spül- und Reinigungsmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass sie Hydroxymischether der Formel (I) enthalten, in der R2für einen Methylrest, R3 für Wasserstoff steht.3. Dishwashing and cleaning agent according to claim 1 or 2, characterized in that they contain hydroxy mixed ethers of the formula (I) in which R 2 is a methyl radical, R 3 is hydrogen.
4. Spül- und Reinigungsmittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sie Hydroxymischether der Formel (I) enthalten, wobei x für die Zahlen 1 bis 3 und y für 10 bis 25 stehen. 4. Detergent and cleaning agent according to one of claims 1 to 3, characterized in that they contain hydroxy mixed ethers of the formula (I), where x represents the numbers 1 to 3 and y represents 10 to 25.
5. Spül- und Reinigungsmittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie Alkyl- und/oder Alkenyloligoglykoside der Formel (II) enthalten, in der R5 für einen Alkylrest mit 6 bis 16 Kohlenstoffatomen steht.5. Dishwashing and cleaning agent according to one of claims 1 to 4, characterized in that they contain alkyl and / or alkenyl oligoglycosides of the formula (II) in which R 5 represents an alkyl radical having 6 to 16 carbon atoms.
6. Spül- und Reinigungsmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass sie Alkyl- und/oder Alkenyloligoglykoside der Formel (II) enthalten, in der p für Zahlen von 1 bis 3 steht.6. Detergent and cleaning agent according to one of claims 1 to 5, characterized in that they contain alkyl and / or alkenyl oligoglycosides of the formula (II) in which p represents numbers from 1 to 3.
7. Spül- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, dass sie - berechnet als Aktivsubstanz, bezogen auf die Mittel - 0,01 bis 25 Gew.-% Hydroxymischether der Formel (I) enthalten.7. detergent and cleaning agent according to claim 1, characterized in that they contain - calculated as active substance, based on the agent - 0.01 to 25 wt .-% hydroxy mixed ether of formula (I).
8. Spül- und Reinigungsmittel nach Anspruch 1 , dadurch gekennzeichnet, dass sie - berechnet als Aktivsubstanz, bezogen auf die Mittel - 0,01 bis 30 Gew.-% Alkyl- und/oder Alkenyloligoglykoside der Formel (II) enthalten.8. Dishwashing and cleaning agent according to claim 1, characterized in that they contain - calculated as the active substance, based on the agent - 0.01 to 30 wt .-% alkyl and / or alkenyl oligoglycosides of the formula (II).
9. Spül- und Reinigungsmittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass sie weitere nichtionische Tenside enthalten, vorzugsweise ausgewählt aus der Gruppe, die gebildet wird von Alkoxylaten von Alkanolen, endgruppenverschlossenen Alkoxylaten von Alkanolen ohne freie OH- Gruppen, alkoxylierten Fettsäureniedrigalkylestern und Aminoxiden.9. Detergent and cleaning agent according to one of claims 1 to 8, characterized in that they contain further nonionic surfactants, preferably selected from the group formed by alkoxylates of alkanols, end-capped alkoxylates of alkanols without free OH groups, alkoxylated fatty acid lower alkyl esters and amine oxides.
10. Spül- und Reinigungsmittel nach Anspruch 9, dadurch gekennzeichnet, dass sie - berechnet als Aktivsubstanz, bezogen auf die Mittel - 0,1 bis 15 Gew,-% weitere nichtionische Tenside enthalten.10. Rinsing and cleaning agent according to claim 9, characterized in that they contain - calculated as active substance, based on the agent - 0.1 to 15% by weight of further nonionic surfactants.
11. Spül- und Reinigungsmittel nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass sie als weitere Komponente anionische Tenside enthalten, vorzugsweise ausgewählt aus der Gruppe, die gebildet wird von Alkyl- und/oder Alkenylsulfaten, Alkylethersulfate, Alkylbenzolsulfonate, Monoglycerid- (ether)sulfate und Alkansulfonate.11. Detergent and cleaning agent according to one of claims 1 to 10, characterized in that they contain anionic surfactants as a further component, preferably selected from the group consisting of alkyl and / or alkenyl sulfates, alkyl ether sulfates, alkylbenzenesulfonates, monoglyceride ( ether) sulfates and alkanesulfonates.
12. Spül- und Reinigungsmittel nach Anspruch 11, dadurch gekennzeichnet, dass sie - berechnet als Aktivsubstanz, bezogen auf die Mittel - 0,1 bis 20 Gew.-% anionische Tenside enthalten.12. Detergent and cleaning agent according to claim 11, characterized in that they contain - calculated as active substance, based on the agent - 0.1 to 20 wt .-% anionic surfactants.
13. Spül- und Reinigungsmittel nach Anspruch 1 , dadurch gekennzeichnet, dass sie in Form von wässrigen Lösungen vorliegen. 13. Detergent and cleaning agent according to claim 1, characterized in that they are in the form of aqueous solutions.
14. Spül- und Reinigungsmittel nach Anspruch 13, dadurch gekennzeichnet, dass der pH-Wert zwischen 4 bis 6,5 liegt.14. Dishwashing and cleaning agent according to claim 13, characterized in that the pH is between 4 to 6.5.
15. Spül- und Reinigungsmittel nach Anspruch 13, dadurch gekennzeichnet, dass der pH- Wert zwischen 7 bis 10 liegt.15. Detergent and cleaning agent according to claim 13, characterized in that the pH is between 7 and 10.
16. Verwendung von Hydroxymischethern in Kombination mit Alkyl- und/oder Alkenyloligoglykosiden zum Spülen und Reinigen von harten Oberflächen. 16. Use of hydroxy mixed ethers in combination with alkyl and / or alkenyl oligoglycosides for rinsing and cleaning hard surfaces.
EP01946883A 2000-01-28 2001-01-19 Rinsing and cleaning agents Expired - Lifetime EP1250408B1 (en)

Applications Claiming Priority (3)

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DE10003752 2000-01-28
DE2000103752 DE10003752A1 (en) 2000-01-28 2000-01-28 Detergent and cleaning agents
PCT/EP2001/000611 WO2001055285A2 (en) 2000-01-28 2001-01-19 Rinsing and cleaning agents

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EP1250408A2 true EP1250408A2 (en) 2002-10-23
EP1250408B1 EP1250408B1 (en) 2009-03-04

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ES2228991T3 (en) * 2001-02-01 2005-04-16 COGNIS DEUTSCHLAND GMBH &amp; CO. KG CLEANING AND CLEANING AGENTS.
DE10153768A1 (en) * 2001-11-02 2003-05-15 Cognis Deutschland Gmbh Hydroxy mixed ethers with polymers
EP1321512A3 (en) * 2001-12-19 2003-09-17 Cognis Deutschland GmbH & Co. KG Rinsing and cleaning composition
DE102005034752A1 (en) * 2005-07-21 2007-01-25 Henkel Kgaa Cleaning and care products with improved emulsifying ability

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DE2432757C2 (en) * 1974-07-08 1984-02-16 Henkel KGaA, 4000 Düsseldorf Polyethylene glycol diethers containing hydroxyl groups suitable as foam inhibitors and their preparation
US5576281A (en) * 1993-04-05 1996-11-19 Olin Corporation Biogradable low foaming surfactants as a rinse aid for autodish applications
WO1999010458A1 (en) * 1997-08-25 1999-03-04 Cognis Deutschland Gmbh Aqueous agents for cleaning hard surfaces
DE19738866A1 (en) * 1997-09-05 1999-03-11 Henkel Kgaa Low-foaming surfactant mixtures with hydroxy mixed ethers
DE19751859A1 (en) * 1997-11-22 1999-07-29 Henkel Ecolab Gmbh & Co Ohg Means for cleaning hard surfaces
EP1155106A2 (en) * 1999-02-22 2001-11-21 The Procter & Gamble Company Cleaning compositions containing selected nonionic surfactants

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WO2001055285A3 (en) 2001-12-13
WO2001055285A2 (en) 2001-08-02

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