EP2108037B1 - Reinigungsmittel für harte oberflächen - Google Patents

Reinigungsmittel für harte oberflächen Download PDF

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Publication number
EP2108037B1
EP2108037B1 EP07857241A EP07857241A EP2108037B1 EP 2108037 B1 EP2108037 B1 EP 2108037B1 EP 07857241 A EP07857241 A EP 07857241A EP 07857241 A EP07857241 A EP 07857241A EP 2108037 B1 EP2108037 B1 EP 2108037B1
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EP
European Patent Office
Prior art keywords
alkyl
agent according
radical
formula
weight
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EP07857241A
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German (de)
English (en)
French (fr)
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EP2108037A1 (de
Inventor
Haitao Rong
Matthias Schweinsberg
Heinz-Dieter Soldanski
Marina Glesius
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL07857241T priority Critical patent/PL2108037T3/pl
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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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3738—Alkoxylated silicones
    • 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
    • C11D1/143—Sulfonic 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention is in the field of detergents for the cleaning of hard surfaces, in particular dishes.
  • the wet or wet hard surfaces are either simply allowed to dry or dried in a further operation, usually with the aid of an absorbent article. Allowing the surfaces to dry is less labor intensive, but takes longer and regularly results in the formation of undesirable visible residues such as stains (water stains) or streaks on glossy (reflective) hard surfaces such as glass, porcelain, ceramic, plastic or metal also to a loss of gloss or dull appearance.
  • rinsing liquor an aqueous solution of a surfactant-containing agent, usually at elevated temperature of, for example, about 45 ° C and then not with a absorbent cloth dried, but allowed to air dry.
  • the rinse liquor is first poured out or poured off and glass or plate for drying.
  • the rinsing liquor layer remaining on the surface of the glass or plate now slowly drains off until, finally, the rinsing liquor layer on the surface has become so thin that it no longer runs off, but only decreases by (self-) drying. The drying also takes place during the process.
  • the international patent application WO 96/18717 A1 discloses a skin mild liquid aqueous cleaner for hard surfaces in the form of a clear microemulsion which removes grease or bad dirt and leaves a shiny appearance on non-rinsed surfaces and contains 14 to 24% by weight of an alkali metal salt of a C12 product.
  • the US 6423661 B1 describes silyl-terminated prepolymers for the preparation of which the OH groups of a polyether polyol, which may have up to eight arms, are reacted with an isocyanate silane.
  • the resulting compounds called prepolymers are for use in adhesives. Use of the prepolymers in detergents is not disclosed.
  • a polyurethane prepolymer having terminal alkoxysilane and hydroxy groups is known.
  • a polyether-diol is first reacted with stoichiometric diisocyanate, and the resulting isocyanate-hydroxy compound is then further treated with an aminosilane to introduce the silyl groups.
  • the described, two-armed polyalkoxylates representing prepolymers are used for the production of sealants and adhesives.
  • the US 2004/0096507 A1 is concerned with six-armed polyethylene glycol derivatives and discloses a completely silyl-terminated derivative which can be prepared starting from sorbitol as a central unit.
  • the polyethylene glycol derivatives described in the document are said to be useful for the preparation of biodegradable polymeric hydrogels and for medical pharmaceutical use, for example, for implants.
  • the object of the present invention was to improve the drying or flow behavior of aqueous surfactant-containing solutions for cleaning hard surfaces, in particular to accelerate the drying or the process.
  • silyl polyalkoxylates of the formula (I) significantly contributes to improving the drying and drainage behavior while maintaining the same rinsing force.
  • the agent according to the invention is suitable as a cleaning agent for hard surfaces (in short: cleaning agent) and in particular as a hand dishwashing detergent (in short: dishwashing detergent).
  • the at least one silyl polyalkoxylate of the formula (I) improves the drying behavior, i. In particular, it increases the drying rate and reduces the formation of residues.
  • the present invention further relates to the use of the agent according to the invention for cleaning hard surfaces, in particular dishes.
  • the agent according to the invention is used for the manual cleaning of hard surfaces, in particular for the manual cleaning of dishes.
  • all other hard surfaces in particular of glass, ceramic, plastic or metal, in household and in trade are also considered hard surfaces.
  • the main advantage of the composition according to the invention or the use according to the invention is the significantly improved drying or flow behavior due to the at least one silyl polyalkoxylate of the formula (I), in particular the high drying speed or short drying time, the high flow rate or short run time and the low flow rate Residue formation and the preserved gloss.
  • Drying here is understood to mean both drying as a whole, in particular until moisture or haptic moisture is not perceptible on the surface, and in particular drying following drainage.
  • agent according to the invention for improving the drying and / or flow behavior.
  • a further advantage of the composition according to the invention or the use according to the invention is the high cleaning action (synonyms: cleaning performance or ability or rinsing action, performance or ability), especially for greasy stains.
  • composition according to the invention is its high storage stability.
  • Multi-armed silyl polyalkoxylates in the context of this invention contain polymer arms which are essentially star-shaped or radially bonded to a central unit.
  • a silyl polyalkoxylate of the formula (I) or a mixture of several of these compounds is used, wherein the weight average molecular weight is from 500 to 50,000, preferably from 1,000 to 20,000, and more preferably from 2,000 to 10,000.
  • the silyl polyalkoxylate preferably contains 0.3 to 10 wt .-%, particularly preferably 0.5 to 5 wt .-% silicon, based on the total weight of the silyl polyalkoxylate.
  • Z preferably represents an at least trihydric, in particular tri-to octahedral, acyclic or cyclic hydrocarbon radical having 3 to 12 carbon atoms, where the radical may be saturated or unsaturated and in particular also aromatic.
  • Z is particularly preferably the trivalent radical of glycerol or the trihydric to hexahydric radical of a sugar, for example the hexavalent radical of sorbitol or the octahedral radical of sucrose.
  • the x-valent radical of one of the abovementioned polyols is to be understood as meaning that molecule fragment which remains from the polyol after removal of the hydrogen atoms from x alcoholic or phenolic hydroxyl groups.
  • Z can stand for any central unit which is known from the literature for the preparation of star-shaped (pre) polymers.
  • n 0, 1 or 2 and m is a number from 3 to 8.
  • A is preferably selected from poly-C 2 -C 4 -alkylene oxides, more preferably a (co) polymer of ethylene oxide and / or propylene oxide, in particular a copolymer having a propylene oxide content of up to 60% by weight, preferably up to to 30 wt .-% and particularly preferably of up to 20 wt.%, Which may be random and / or block copolymers.
  • A is - (CHR 3 -CHR 4 -O) p -, where R 3 and R 4 independently of one another are hydrogen, methyl or ethyl and p is an integer of 2 to 10,000 means.
  • B is in particular a chemical bond or a bivalent, low molecular weight organic radical having preferably 1 to 50, in particular 2 to 20 carbon atoms.
  • divalent low molecular weight organic radicals are short-chain aliphatic and heteroaliphatic radicals such as - (CH 2 ) 2 -, - (CH 2 ) 3 -, -C (O) -NH- (CH 2 ) 3 - and -C (O) -NH-X-NH-C (O) -NH- (CH 2 ) 3 -, wherein X is a bivalent aromatic radical such as the phenylene radical or an alkylidene radical.
  • B is a bond or the radical -C (O) -NH- (CH 2 ) 3 -.
  • R 1 and R 2 independently of one another are methyl or ethyl, and r is 2 or 3.
  • radicals -Si (OR 1 ) r (R 2 ) 3-r are dimethylethoxysilyl, dimethylmethoxysilyl, diisopropylethoxysilyl, methyldimethoxysilyl
  • trimethoxysilyl and triethoxysilyl radicals are most preferred.
  • R 1 and R 2 are the same and are methyl or ethyl.
  • r stands for the number 3.
  • the sum m + n is preferably 3 to 50, in particular 3 to 10 and particularly preferably 3 to 8, and coincides with the number of arms which is bound in the compound (I) to the central unit Z.
  • the central unit therefore preferably has 3 to 50, in particular 3 to 10 and particularly preferably 3 to 8, oxygen atoms which serve as attachment points for the arms.
  • n is 0.
  • the ratio n / m is between 99/1 and 1/99, preferably 49/1 and 1/49, and especially 9/1 and 1 /.
  • a mixture of at least two, in particular two to four, different multi-armed silyl polyalkoxylates of the formula (I) is used.
  • the at least two different multi-armed silyl polyalkoxylates differ in the number of their arms.
  • a first silyl polyalkoxylate having 3 to 6 arms is combined with a second silyl polyalkoxylate having 6 to 10 arms.
  • two different multi-arm silyl polyalkoxylates are used, they are generally present in a quantitative ratio of from 99: 1 to 1:99, preferably from 49: 1 to 1:49, and more preferably from 9: 1 to 1: 9.
  • the agent according to the invention further contains at least one hydrolyzable silicic acid derivative.
  • Hydrolyzable silicic acid derivatives are to be understood as meaning in particular the esters of orthosilicic acid, in particular the tetraalkoxysilanes and very particularly preferably tetraethoxysilane.
  • the quantitative ratio of silyl polyalkoxylate or silyl polyalkoxylate mixture to the at least one hydrolyzable silicic acid derivative 90:10 to 10:90, preferably 50:50 to 10:90, and especially 40:60 to 20:80.
  • the at least one silyl polyalkoxylate of the formula (I) is usually used in an amount of 0.01 to 10 wt .-%, preferably 0.05 to 5 wt .-%, and particularly preferably 0.1 to 2.5 wt. %, based on the total weight of the composition.
  • the US 2004/0096507 A1 is concerned with six-armed polyethylene glycol derivatives and discloses a fully silyl-terminated derivative which can be prepared starting from sorbitol as a central unit and which falls under the general formula (I) of the present invention.
  • Suitable polyalkoxylate precursors for the preparation of the silyl polyalkoxylates used according to the invention are in turn polyaromatic polyalkoxylates which already have the above-described multi-arm structure and which each have a hydroxyl group at the ends of the polymer arms which is partially or completely group (n) -B -Si (OR 1 ) r (R 2 ) 3-r can or can.
  • the polyalkoxylate precursors of the silyl polyalkoxylates used according to the invention can be represented by the general formula (II) Z- (A-OH) m + n (II) represent, wherein Z, A, m and n have the same meaning as previously described for the compounds of formula (I).
  • suitable polyalkoxylate precursors are known from the literature under the name star-shaped or multi-arm polyether polyols. These polyalkoxylate precursors are prepared by polymerization of the appropriate monomers, especially ethylene oxide and / or propylene oxide, using polyfunctional small molecules such as glycerol or sorbitol as initiator. Examples of polyhydric polyether polyols ethoxylates or propoxylates of glycerol, sucrose and sorbitol, as described in the patent US 6423661 are described.
  • Suitable polyalkoxylate precursors are also commercially available in part.
  • An example of this is Voranol 4053, a polyether polyol (poly (ethylene oxide-co-propylene oxide)) from DOW Chemicals. It is a mixture of two different polyether polyols, consisting of a 3-arm polyether polyol with glycerol as the central unit and an 8-arm polyether polyol with cane sugar as the central unit.
  • the arms represent random copolymers of about 75% EO and about 25% PO, the OH functionality (hydroxy end groups) is an average of 6.9 at a weight average molecular weight of about 12000.
  • Examples are tetraalkoxy silanes such as tetramethyl silicate and Tetraethyl silicate, (meth) acrylate silanes such as (3-methacryloxypropyl) trimethoxysilane, (methacryloxymethyl) triethoxysilane, (meth-acryloxymethyl) methyldimethoxysilane and (3-acryloxypropyl) trimethoxysilane, isocyanato-silanes such as (3-isocyanatopropyl) trimethoxysilane, (3-isocyanato -propyl) triethoxysilane, (isocyanatomethyl) methyldimethoxysilane and (isocyanatomethyl) trimethoxysilane, aldehyde-silanes such as triethoxysilylundecanal and triethoxysilylbutyraldehydes, epoxy-silanes such as (3-glycidoxypropyl)
  • Tetraalkoxysilanes, isocyanato-silanes or anhydride-silanes, but especially tetraalkoxysilanes, are particularly preferably reacted with polyhydric polyalkoxylate precursors of the general formula (II).
  • the group B is in such a case, for example, exclusively in a bond, or it comprises, when an isocyanatosilane was used as a functional silane, together with the terminal oxygen atom of group A, for example, a urethane group and the atomic group, in the starting isocyanatosilane between the isocyanato group and the silyl group stands.
  • group A for example, a urethane group and the atomic group
  • anhydride silanes for example 3- (triethoxysilyl) propylsuccinic
  • Group B in such a case, together with the terminal oxygen atom of group A, comprises an ester group and the atomic group which in the starting anhydride silane is between the anhydride group and the silyl group.
  • multi-arm silyl polyalkoxylates of the general formula (I) used according to the invention which carry both hydroxy and -B-Si (OR 1 ) r (R 2 ) 3-r groups at the ends of their arms, preference is given to this has proceeded so that a polyalkoxylate precursor of the general formula (II) is reacted with a substoichiometnschen with respect to the totality of the terminal hydroxy groups amount of a functional silane, ie there are as described above first -B-Si (OR 1 ) r (R 2 ) Introduced 3-r groups, but not all terminal hydroxyl groups in the polyhydric polyalkoxylate precursor reacted.
  • the other components present in the aqueous composition according to the invention in addition to the at least one silyl polyalkoxylate are to be selected according to their type and the amount used in such a way that no undesired interactions with the silyl polyalkoxylate occur.
  • fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 5 to 26 carbon atoms.
  • the former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them.
  • the oxo-alcohols or their derivatives which are obtainable, for example, by Roelen's oxo synthesis, can also be used correspondingly.
  • Suitable alcohols are also Lial® types and the less branched Neodol® types (Shell Corp.). If one speaks of fatty acid alkyl or tallow alkyl radicals, this includes the alkyl radicals which are derived by hydrogenation of the respective acid.
  • alkaline earth metal as counterions for monovalent anions are mentioned, this means that the alkaline earth metal, of course, is present only in half - sufficient to charge balance - amount of substance as the anion.
  • the INCI names are the " International Cosmetic Ingredient Dictionary and Handbook, Seventh Edition (1997 issued by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101, 17 th Street NW, Suite 300, Washington, DC, 20036, USA, and more than 9,000 INCI names and references to more than 37,000 Includes trade names and technical names including associated distributors from over 31 countries
  • the International Cosmetic Ingredient Dictionary and Handbook assigns one or more chemical classes to the ingredients, such as “Polymeric Ethers”, and one or more functions, for example “Surfactants - Cleansing Agents", to which it will be further explained, and where appropriate also referred to below.
  • the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.
  • composition of the invention comprises surfactants in a total amount of usually 0.5 to 60 wt .-%, preferably 1 to 55 wt .-%, in particular 5 to 50 wt .-%, particularly preferably 10 to 45 wt .-% and most preferably 15 to 40% by weight. Particularly preferred proportions are, for example, 18, 25, 32 and / or 36 wt .-%.
  • composition according to the invention in particular for improving cleaning action, flow behavior and / or drying behavior, may additionally comprise one or more further anionic surfactants, nonionic surfactants and / or cationic surfactants.
  • alkyl ether sulfates, alkyl and / or aryl sulfonates and / or alkyl sulfates and the other anionic surfactants are usually used as alkali metal, alkaline earth metal and / or mono-, di- or trialkanolammonium salt and / or in the form of their with the corresponding alkali metal hydroxide, Alkaline earth metal hydroxide and / or mono-, di- or trialkanolamine used in situ to be neutralized corresponding acid.
  • alkali metals potassium and sodium in particular, as alkaline earth metals calcium and magnesium in particular, and as alkanolamines mono-, di- or triethanolamine.
  • Particularly preferred are the sodium salts.
  • Alkyl ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • the person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols, ie with aliphatic straight-chain or one or more branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably straight-chain, acyclic, saturated, alcohols having 6 to 22, preferably 8 to 18, in particular 10 to 16 and particularly preferably 12 to 14 carbon atoms.
  • n 1 to 30, preferably 0.3 to 20, especially 0.3 to 10, particularly preferably 0.3 to 5).
  • alkoxylation is the use of mixtures of alkylene oxides, preferably the mixture of Ethylene oxide and propylene oxide.
  • EO ethylene oxide units
  • the agent according to the invention contains one or more alkyl ether sulfates in an amount of usually 1 to 50% by weight, preferably 3 to 40% by weight, in particular more than 6 to 30% by weight, particularly preferably 8 to 20% by weight, most preferably 10 to 16% by weight.
  • the alkyl sulfonates usually have an aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated, alkyl radical having 6 to 22, preferably 9 to 20, in particular 11 to 18 and more preferably 13 to 17 carbon atoms.
  • suitable alkyl sulfonates are the saturated alkanesulfonates, the unsaturated olefin sulfonates and the ether sulfates derived formally from the alkoxylated alcohols on which the alkyl ether sulfates are based, in which terminal ethersulfonates ( n- ether sulfonates) having a sulfonate function bound to the polyether chain are present Ethersulfonates (i-ether sulfonates) with the alkyl-linked sulfonate function.
  • alkanesulfonates in particular alkanesulfonates having a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na C 13-17 alkanesulfonate ( INCI Sodium C14-17 Alkyl Sec Sulfonate).
  • Preferred arylsulfonates are alkylbenzenesulfonates, where the alkyl radicals are branched and unbranched chains with C1-C20, preferably C2-C18, more preferably C6-C16 and most preferably C8-C12. Particularly preferred examples here are LAS and / or cumene sulfonate.
  • the composition according to the invention contains one or more alkyl and / or arylsulfonates in an amount of usually 0.1 to less than 50% by weight, preferably 0.1 to 30% by weight, in particular 1 to less than 14% by weight %, more preferably 2 to 10% by weight, most preferably 4 to 8% by weight.
  • alkyl sulfates such as fatty alcohol sulfates can be used.
  • Suitable alkyl sulfates are sulfates of saturated and unsaturated fatty alcohols with C 6 -C 22 , preferably C 10 -C 18 and more preferably C 11 -C 16 .
  • Particularly suitable alkyl sulfates are those with native C-step C12-14-16 and / or petrochemical C-step C12-13, C14-C15, which are preferably present in the agent in amounts of 0 to 15%, preferably 0-10% preferably 0-8% may be included.
  • amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include betaines, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the betaines are preferred in the context of the teaching according to the invention.
  • the composition according to the invention comprises one or more amphoteric surfactants in an amount of usually 0.1 to 20% by weight, preferably 1 to 15% by weight, in particular 2 to 12% by weight, particularly preferably 3 to 10% by weight .-%, most preferably 4 to 8 wt .-%.
  • Preferred amphoteric surfactants are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id), R 1 -N + (CH 3 ) 2 -CH 2 COO - (Ia) R 1 -CO-NH (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 COO - (Ib) R 1 is -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 - (Ic) R 1 -CO-NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 - (Id) in which R 1 has the same meaning as in formula I.
  • amphoteric surfactants are the carbo-betaines, in particular the carbo-betaines of the formula (Ia) and (Ib), most preferably the alkylamido-betaines of the formula (Ib).
  • betaines and sulfobetaines are the following compounds designated as INCI : almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, caprylic / capramidopropyl betaines, carnitines, cetyl betaines, cocamidoethyl betaines, cocamidopropyl Betaines, cocamidopropyl hydroxysultaines, coco-betaines, coco-hydroxysultaines, coco / oleamidopropyl betaines, coco-sultaines, decyl betaines, dihydroxyethyl oleyl glycinates, dihydroxyethyl soy glycinates, dihydroxyethy
  • alkylamidoalkylamines are the following named according to INCI compounds: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium laureth 5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodia
  • alkyl-substituted amino acids are the aminopropionates according to formula (IVa), R 13 -NH-CH 2 CH 2 COOM '(IVa) in which R 13 and M 'have the same meaning as in formula (IV).
  • Illustrative alkyl substituted amino acids are the following INCI compounds: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA Myrista
  • Acylated amino acids are amino acids, in particular the 20 natural ⁇ -amino acids which carry on the amino nitrogen the acyl radical R 19 CO of a saturated or unsaturated fatty acid R 19 COOH, where R 19 is a saturated or unsaturated C 6-22 alkyl radical, preferably C 8-18 -Alkyl, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical.
  • the acylated amino acids can also be used as the alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt.
  • acylated amino acids are the acyl derivatives summarized in accordance with INCI under Amino Acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
  • a combination of two or more different amphoteric surfactants in particular a binary Amphotensidkombination is used.
  • the amphoteric surfactant combination preferably contains at least one betaine, in particular at least one alkylamidobetaine, more preferably cocoamidopropylbetaine.
  • amphoteric surfactants preferably contains at least one amphoteric surfactant is selected from group comprising Natruimcarboxyethylkokosphosphoethylimidazolin (Phosphoteric ® TC-6), C 8/10 -Amidopropylbetain (INCI caprylic / Capramidopropyl Betaine, Betaine Tego ® 810), N-2-hydroxyethyl-N-carboxymethyl -fettklamido-ethylamimNa (Rewoteric ® AMV) and N-caprylic / capric amidoethyl-N-ethyl-propionate-Na (Rewoteric AMVSF ®) and the betaine 3- (3-cocoamido-propyl) dimethylammonium-2-hydroxypropanesulfonate (INCI sultaines; Rewoteric AM CAS ®) and the Alkylamidoalkylamin N-
  • the agent according to the invention contains one or more amphoteric surfactants in an amount of from 1 to 15 and in particular from 5 to 10% by weight.
  • composition of the invention may additionally comprise one or more other anionic surfactants, usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2% by weight, most preferably 0.5 to 1.5% by weight, for example 1% by weight.
  • anionic surfactants usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2% by weight, most preferably 0.5 to 1.5% by weight, for example 1% by weight.
  • Suitable further anionic surfactants are, in particular, aliphatic sulfates such as monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignin sulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.
  • aliphatic sulfates such as monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignin sulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taur
  • Suitable further anionic surfactants are also anionic gemini surfactants having a diphenyl oxide basic structure, 2 sulfonate groups and an alkyl radical on one or both benzene rings according to the formula - O 3 S (C 6 H 3 R) O (C 6 H 3 R ') SO 3 - in which R is an alkyl radical with, for example, 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax ® Dry hydrotropes Powder with C 16 -Alkytrest (s); INCI Sodium Hexyldiphenyl ether sulfonates, Disodium decyl phenyl ether disulfonates, Disodium lauryl phenyl ether disulfonates, Disodium Cetyl phenyl ether disulfonates) and fluorinated anionic surfactants, in particular perfluorinated alkylsulfonates such as ammonium C 9/10 -Perfluoroal
  • Particularly preferred further anionic surfactants are the anionic sulfosuccinic acid surfactants sulfosuccinates, sulfosuccinamates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates.
  • the sulfosuccinates are the salts of the monoesters and diesters of sulfosuccinic acid HOOCCH (SO 3 H) CH 2 COOH, while the sulfosuccinamates are the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides are the salts of the diamides of sulfosuccinic acid.
  • anionic surfactants A. Domsch and B. Irrgang in Anionic surfactants: organic chemistry (edited by HW Stache; Surfactant science series; volume 56; ISBN 0-8247-9394-3; Marcel Dekker, Inc., New York 1996, pp. 501-549 ).
  • the salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, more preferably sodium or potassium salts Ammonium salts, most preferably sodium salts.
  • one or both carboxyl groups of the sulfosuccinic acid is preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols having 4 to 22, preferably 6 to 20, especially 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified.
  • esters of unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols in particular unbranched, saturated fatty alcohols and / or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols having a degree of alkoxylation of 1 to 20, preferably 1 to 15, in particular 1 to 10, more preferably 1 to 6, most preferably 1 to 4.
  • the monoesters are preferred in the context of the present invention over the diesters.
  • a particularly preferred sulfosuccinate is Sulfobernsteinklarylpolyglykolester-di-sodium salt (lauryl EO sulfosuccinate, di-sodium salt; INCI Disodium Laureth Sulfosuccinate), for example, as Tego ® sulfosuccinate F 30 (Goldschmidt) with a sulfosuccinate of 30 parts by weight % is commercially available.
  • one or both form carboxyl groups of the sulfosuccinic acid preferably with a primary or secondary amine having one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals having 4 to 22 , preferably 6 to 20, in particular 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms carries, a carboxylic acid amide.
  • Particular preference is given to unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals.
  • sulfosuccinates designated under INCI and sulfosuccinamates, which are described in the International Cosmetic Ingredient Dictionary and Handbook detail are: ammonium dinonyl sulfosuccinates, Ammonium Lauryl Sulfosuccinate, diammonium dimethicone copolyol sulfosuccinates, diammonium lauramido MEA sulfosuccinates, diammonium lauryl sulfosuccinates, diammonium oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Dioctyl sulfosuccinate
  • Preferred anionic sulfosuccinic are imidosuccinate, mono-Na-sulfosuccinic acid diisobutyl ester (Monawet MB ® 45), mono-Na-sulfosuccinic acid di-octyl ester (Monawet MO-84 ® R2W, Rewopol SB ® DO 75), mono-Na sulfosuccinic acid di-tridecyl (Monawet ® MT 70) Fettalkoholpolyglykolsulfosuccinat-Na-NH 4 salt (sulfosuccinate S-2), di-Na-sulfosuccinic acid mono-C 12/14 3EO ester (Texapor ® SB-3) , Natruimsulfobernsteinklasooctylester (Texin ® DOS 75) and di-Na-sulfosuccinic mono-C 12/18 esters -
  • the agent according to the invention contains as anionic sulfosuccinic acid surfactants one or more sulfosuccinates, sulfosuccinamates and / or sulfosuccinamides, preferably sulfosuccinates and / or sulfosuccinamates, in particular sulfosuccinates, in an amount of usually 0.001 to 5% by weight, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1.5 wt .-%, for example 1 wt .-%.
  • anionic sulfosuccinic acid surfactants one or more sulfosuccinates, sulfosuccinamates and / or sulfosuccinamides, preferably sulfosuccinates and / or s
  • composition according to the invention may additionally contain one or more nonionic surfactants, usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0 , 2 to 2% by weight, most preferably 0.5 to 1.5% by weight, for example 1% by weight.
  • nonionic surfactants usually in an amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt .-%, particularly preferably 0 , 2 to 2% by weight, most preferably 0.5 to 1.5% by weight, for example 1% by weight.
  • Nonionic surfactants in the context of the invention are alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, endgroup-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also suitable are block polymers of ethylene oxide and propylene oxide as well as fatty acid alkanolamides and fatty acid polyglycol ethers. Important classes of nonionic surfactants according to the invention are furthermore the amine oxides and the sugar surfactants, in particular the alkyl polyglucosides.
  • Suitable amine oxides are the following compounds designated as INCI : almondamidopropylamine oxides, babassuamidopropylamine oxides, behenamine oxides, cocamidopropyl amine oxides, cocamidopropylamine oxides, cocamine oxides, coco-morpholine oxides, decylamine oxides, decyltetradecylamine oxides, diaminopyrimidines oxides, dihydroxyethyl C8-10 alkoxypropylamines oxides , Dihydroxyethyl C9-11 alkoxypropylamines oxides, dihydroxyethyl C12-15 alkoxypropylamines oxides, dihydroxyethyl cocamine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamines oxides, dihydroxyethyl tallowamine oxides, hydrogenated palm kernel, amine oxides, hydrogenated tallowamine oxides, hydroxyethyl
  • Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of the alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerolamides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides, as described, for example, in US Pat WO 97/00609 and references cited therein (pages 4 to 12), to which reference is made in this regard and the contents of which are hereby incorporated by reference into this application.
  • sugar surfactant classes include, for example, the sugar surfactant classes of the alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerolamides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides, as described, for example
  • Preferred sugar surfactants within the scope of the teaching according to the invention are the alkyl polyglycosides and the sugar amides and their derivatives, in particular their ethers and esters.
  • the ethers are the products of the reaction of one or more, preferably one, sugar hydroxy group with a compound containing one or more hydroxy groups, for example C 1-22 alcohols or glycols such as ethylene and / or propylene glycol, the sugar hydroxy group also being polyethylene glycol - And / or polypropylene glycol can carry.
  • the esters are the reaction products of one or more, preferably one, sugar hydroxy group with a carboxylic acid, in particular a C 6-22 fatty acid.
  • Particularly preferred sugar amides satisfy the formula R'C (O) N (R ") [Z], in which R 'is a linear or branched, saturated or unsaturated acyl radical, preferably a linear unsaturated acyl radical, having 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, R "is a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferred 8 to 14 carbon atoms, a C 1-5 -alkyl radical, in particular a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert- butyl or n-pentyl radical, or hydrogen and Z is a sugar radical, ie a monosaccharide residue.
  • Particularly preferred sugar amides are the amides of glucose, the glucamides, for example la
  • alkyl polyglycosides are particularly preferred sugar surfactants within the scope of the teaching according to the invention and preferably satisfy the general formula R i O (AO) a [G] x in which R 'is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar residue and x for a number from 1 to 10 and AO for an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a represent the average degree of alkoxylation of 0 to 20.
  • R i O (AO) a [G] x in which R 'is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar residue and x for a number from 1 to
  • the group (AO) a may also contain different alkyleneoxy units, for example ethyleneoxy or propyleneoxy units, in which case a is the average total degree of alkoxylation, ie the sum of degree of ethoxylation and degree of propoxylation.
  • alkyl radicals R 1 of the APG are linear unsaturated radicals having the stated number of carbon atoms.
  • APG are nonionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry.
  • alkyl glycosides having a mean degree of oligomerization x of 1.1 to 3.0 are used. From an application point of view, those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred.
  • the glycosidic sugar used is preferably xylose, but especially glucose.
  • the alkyl or alkenyl radical R ' can be derived from primary alcohols having 8 to 18, preferably 8 to 14, carbon atoms.
  • Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, for example in the course of the hydrogenation of technical fatty acid methyl esters or in the course of hydrogenation of aldehydes from ROELEN's oxo synthesis.
  • the alkyl or alkenyl radical R ' is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • lauryl alcohol myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • elaidyl alcohol petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.
  • preferred alkyl polyglycosides are, for example, C 8-10 and C 12-14 alkyl polyglucoside having a DP degree of 1.4 or 1.5, especially C 8-10 alkyl-1,5-glucoside and C 12-14 alkyl-1,4-glucoside.
  • composition according to the invention may additionally contain one or more cationic surfactants (cationic surfactants, INCI quaternary ammonium compounds), usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 to 3% by weight .%, Particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1.5 wt .-%, for example 1 wt .-%.
  • cationic surfactants cationic surfactants, INCI quaternary ammonium compounds
  • Preferred cationic surfactants are the quaternary surface-active compounds, in particular having an ammonium, sulfonium, phosphonium, iodonium or arsonium group, such as, for example KH Wallrobußer in "Practice of Sterilization, Disinfection - Conservation: Germ Identification - Plant Hygiene” (5th edition - Stuttgart, New York: Thieme, 1995 ) as antimicrobial agents.
  • KH WallPS in "Practice of Sterilization, Disinfection - Conservation: Germ Identification - Plant Hygiene” (5th edition - Stuttgart, New York: Thieme, 1995 ) as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • Particularly preferred cationic surfactants in addition to the quaternary ammonium compounds of the formula I used as drying and gloss additives, are the quaternary, in part antimicrobial ammonium compounds (QAV, INCI quaternary ammonium compounds) according to the general formula (R I ) (R II ) (R III ) (R IV ) N + X - , in which R 1 to R IV are identical or different C 1-22 -alkyl radicals, C 7-28 -aralkyl radicals or heterocyclic radicals, where two or im In the case of an aromatic inclusion, as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X - are halide ions, sulfate ions, hydroxide ions or similar anions.
  • at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecy
  • Suitable QAVs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B ( m, p- dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyldodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No.
  • benzalkonium chloride N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5
  • benzalkone B m, p- dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78 -6
  • benzetonium chloride N, N-dimethyl -N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No. 121-54-0
  • dialkyl dimethyl such as di- n decyl-dimethyl ammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyl-dimethylammoniumchloric, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No.
  • QACs are the benzalkonium chlorides having C 8 -C 18 -alkyl radicals, in particular C 12 -C 14 -alkyl-benzyl-dimethylammonium chloride.
  • a particularly preferred QAC Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate: Rewoquat CPEM ®).
  • antimicrobial cationic surfactants with the anionic surfactants contained according to the invention as far as possible anionic surfactant compatible and / or cationic surfactant as little as possible or omitted in a particular embodiment of the invention entirely on antimicrobial cationic surfactants.
  • Parabens, benzoic acid and / or benzoate, lactic acid and / or lactates can be used as antimicrobial substances. Particularly preferred are benzoic acid and / or lactic acid.
  • the water content of the aqueous composition according to the invention is usually 20 to 99 wt .-%, preferably 40 to 90 wt .-%, in particular 50 to 85 wt .-%, particularly preferably 55 to 80 wt.%.
  • the agent according to the invention may advantageously additionally contain one or more water-soluble organic solvents, usually in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, in particular 2 to 15% by weight, more preferably 4 to 12% by weight, most preferably 6 to 10% by weight.
  • the solvent is used in the context of the teaching of the invention as needed in particular as a hydrotrope, viscosity regulator and / or cold stabilizer. It acts solubilizing in particular for surfactants and electrolyte as well as perfume and dye and thus contributes to their incorporation, prevents the formation of liquid-crystalline phases and has a share in the formation of clear products.
  • the viscosity of the agent according to the invention decreases with increasing amount of solvent. However, too much solvent can cause excessive viscosity drop. Finally, as the amount of solvent increases, the clouding and clearing point of the composition according to the invention decreases.
  • Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C 1-20 -hydrocarbons, preferably C 2-15 -hydrocarbons, having at least one hydroxy group and optionally one or more ether functions COC, ie the carbon atom chain interrupting oxygen atoms.
  • Preferred solvents are the optionally unilaterally with a C 1-6 alkanol etherified - C 2-6 alkylene glycols and poly-C 2-3 alkylene glycol ethers having an average of 1 to 9 identical or different, preferably the same, alkylene glycol groups per molecule as well C 1-6 -alcohols, preferably ethanol, n-propanol or iso -propanol, in particular ethanol.
  • Exemplary solvents are the following INCI compounds: alcohol (ethanol), buteth-3, butoxy diglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyloctanol, diethylene glycol, dimethoxy diglycol, dimethyl ether, Dipropylene glycol, ethoxydiglycol, ethoxyethanol, ethyl hexanediol, glycol, hexanediol, 1,2,6-hexanetriol, hexyl alcohol, hexylene glycol, isobutoxypropanol, isopentyldiol, isopropyl alcohol ( iso -propanol), 3-methoxybutanol, methoxy diglycol, methoxyethanol, methoxyisopropanol, Methoxymethylbutanol, Methoxy PEG-10, Methyl
  • Particularly preferred solvents are the unilaterally etherified with a C 1-6 alkanol poly-C 2-3 alkylene glycol having an average of 1 to 9, preferably 2 to 3, ethylene or propylene glycol, for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).
  • Most preferred solvents are the C 2-3 alcohols ethanol, n-propanol and / or iso -propanol, especially ethanol.
  • solubilizer in particular for perfume and dyes, for example, alkanolamines and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical can be used in addition to the solvents described above.
  • the agent according to the invention for further improving the drainage and / or drying behavior may contain one or more further additives from the group of surfactants, polymers and builders, usually in one Amount of 0.001 to 5 wt .-%, preferably 0.01 to 4 wt .-%, in particular 0.1 to 3 wt.%, Particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1 , 5 wt .-%, for example, 1 wt .-%.
  • Surfactants suitable as additives are certain of the amphoteric surfactants already described above, further anionic surfactants, nonionic surfactants and cationic surfactants, which are repeated at this point.
  • the content of surface-active additives is preferably to be chosen such that the total surfactant content is in the above-stated quantitative ranges.
  • amphoteric surfactants are, in particular Natriumcarboxyethylkokosphosphoethylimidazolin (Phosphoteric ® TC-6), C 8/10 -Amidopropylbetain (INCI caprylic / Capramidopropyl Betaine, Betaine Tego ® 810), N-2-hydroxyethyl-N-ethylamine carboxymethylfettklastedreamido-Na (Rewoteric ® AMV) and N-caprylic / capric amidoethyl-N-ethyletherpropionat-Na (Rewoteric AMVSF ®) and the betaine 3- (3-cocoamido-propyl) dimethylammonium-2-hydroxypropane (INCI sultaines; Rewoteric AM CAS ®) and the Alkylamidoalkylamin N- [N '(N "-2-hydroxyethyl-N" -carboxyeth
  • anionic surfactants which are suitable as additives are, in particular, anionic gemini surfactants having a diphenyloxide basic structure, 2 sulfonate groups and one alkyl radical on one or the other both benzene rings according to the formula -O 3 S (C 6 H 3 R) O (C 6 H 3 R ') SO 3 - , in which R is an alkyl radical having, for example, 6, 10, 12 or 16 carbon atoms and R' is R 2 or H (Dowfax ® Dry Powder hydrotropes with C 16 alkyl radical (s); INCI Sodium Hexyldiphenyl ether sulfonates, disodium decyl phenyl ether disulfonates, Disodium lauryl phenyl ether disulfonates, Disodium Cetyl phenyl ether disulfonates) and the fluorinated anionic surfactants ammonium C 9/10 -Perfluoroalkylsulfonat (
  • suitable nonionic surfactants are in particular C 10 dimethyl amine oxide (Ammonyx ® DO), C 10/14 -fatty alcohol + 1,2PO + 6,4EO (Dehydol ® 980), C 12/14 -fatty alcohol + 6 EO (Dehydol ® LS6) , C 8 fatty alcohol + 1,2P0 + 9E0 (Dehydol ® O10), C 12-18 FAEO ⁇ 7 EO (Dehydol LT 7) FAEO C 12-16 ⁇ 5.5 EO (Dehydol LSS 5.5) FAEO C 9-13 ⁇ 5 EO, FAEO C 10-14 ⁇ 1.2 PO 6.4 + EO, C 16/20 -Guerbetalkohol + 8EO, n-butyl-closed (Dehypon ® G2084), mixture of several n-Butylver tolerateen nonionic surfactants and C 8/10 APG (Dehypon ® Ke 2555) C 8/10 fatty alcohol + 1
  • Suitable as additives further cationic surfactants are particularly compatible with anionic surfactants, cationic surfactants such as quaternary ammonium compounds, for example Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoqual CPEM ®).
  • anionic surfactants such as quaternary ammonium compounds, for example Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoqual CPEM ®).
  • Polymers suitable as additives in particular maleic acid-acrylic acid copolymer, Na salt (Sokalan ® CP 5), modified polyacrylic acid Na-alz (Sokalar ® CP 10), polyvinylpyrrolidone PVP and PVP-N-oxide (Sokalan ® HP 26) are modified polycarboxylate Na-alz (Sokalan ® HP 25) polyalkylene oxide-modified heptamethyltrisiloxane (Silwet ® L-77), polyalkylene oxide-modified heptamethyltrisiloxane (Silwet ® L-7608), polyether (copolymers of polydimethylsiloxanes having ethylene oxide / propylene oxide segments (polyether) preferably water-soluble linear polyether having terminal polyether as Tegopren ® 5840, Tegopren ® 5843, Tegoprer ® 5847, Tegopren ® 5851, Tegopren ® 5863
  • suitable builders are, in particular polyaspartic acid-Na-salt, Ethylendiamintriacetatkokosalkylacetamid (Rewopol ® CHT 12) Methytgtycindiessigcicre-Tri-Na-salt (Trilon ES ® 9964) and acetophosphonic (Turpinal SL ®).
  • Blends with surfactant or polymeric additives show in the case of Monawet MO-84 ® R2W, Tegopren ® 5843 and Tegopren 5863 ® synergism.
  • Tegopren grades 5843 and 5863 is less preferred when applied to hard surfaces of glass, especially glassware, since these can apply silicone surfactants to glass.
  • the additives mentioned are dispensed with.
  • the favorable for the inventive agent viscosity is 20 ° C and a shear rate of 30 s -1 - measured by a viscometer type Brookfield LV DV II and spindle 25 - in the range of 10 to 5000 mPas, preferably 50 to 2000 mPas, in particular 100 to 1000 mPas, more preferably 150 to 700 mPas, most preferably 200 to 500 mPas, for example 300 to 400 mPas.
  • the viscosity of the composition according to the invention can be increased by thickening agents and / or, in particular with a high surfactant content of the composition, can be reduced by solvents, especially with a low surfactant content of the agent.
  • composition according to the invention may additionally contain one or more electrolyte salts and / or one or more polymeric thickeners.
  • Electrolyte salts in the context of the present invention are salts which decompose into their ionic constituents in the aqueous agent according to the invention.
  • the salts in particular alkali metal and / or alkaline earth metal salts, of an inorganic acid, preferably of an inorganic acid from the group comprising the hydrohalic acids, nitric acid and sulfuric acid, in particular the chlorides and sulfates.
  • a particularly preferred electrolyte salt is magnesium sulfate, especially M 9 SO 4 -7H 2 O, also referred to as Epsom salt, and minerally occurring as epsomite.
  • an electrolyte salt can also be used in the form of its corresponding acid / base pair, for example hydrochloric acid and sodium hydroxide instead of sodium chloride.
  • the content of electrolyte salt is usually not more than 8 wt.%, Preferably between 0.1 and 6 wt .-%, particularly preferably between 0.2 and 4 wt.%, In particular between 0.3 and 2 wt .-% and most preferably between 0.5 and 1% by weight, for example 0.7% by weight.
  • Polymeric thickeners for the purposes of the present invention are the polyelectrolytes thickening polycarboxylates, preferably homopolymers and copolymers of acrylic acid, especially acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other conventional thickening polymers.
  • Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, e.g. propoxylated guar, as well as their mixtures.
  • Other polysaccharide thickeners such as starches or cellulose derivatives, may be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g.
  • a preferred polymeric thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15 ⁇ 10 6, and for example, by Fa. Kelco under the trade name Keltrol ®, for example, as a cream powder Ke / Frol ® T (T ransparent) or as white granules Keltrol ® RD (R eadily ispersable D).
  • Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene ( INCI Carbomer), which are also referred to as carboxyvinyl polymers.
  • a polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene ( INCI Carbomer), which are also referred to as carboxyvinyl polymers.
  • Such polyacrylic acids are obtainable inter alia from Fa. BFGoodrich under the tradename Carbopol ®, such as Carbopol ® 940 (molecular weight approximately 4,000,000).
  • Carbopol ® 941 molecular weight approximately 1,250,000
  • Carbopol ® 934 molecular weight approximately 3,000,000).
  • acrylic acid copolymers are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C 1-4 alkanols formed esters (INCI acrylates copolymer), to which example, the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and available, for example from Messrs.
  • Rohm & Haas under the trade names Aculyn ® and Acusol ® are, for example, the anionic non-associative polymers Aculyn ® 33 (crosslinked), Acusol ® 810 and Acusol ® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C 10-30 alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C 1 -4 alkanols formed, esters (INCI acrylates / C10-30 alkyl acrylate crosspolymer) and which are obtainable for example from the company.
  • Aculyn ® 33 crosslinked
  • Acusol ® 810 and Acusol ® 830 CAS 25852-37-3
  • crosslinked high molecular weight acrylic acid copolymers such as those
  • Carbopol ® examples hydrophobized ETD 2623 and Carbopol ® 1382 (INCI acrylates / C10-30 alkyl acrylate Crosspolymer) and Carbopol AQUA ® 30 (formerly Carbopol ® EX 473).
  • the content of polymeric thickener is usually not more than 8 wt .-%, preferably between 0.1 and 7 wt .-%, particularly preferably between 0.5 and 6 wt.%, In particular between 1 and 5 wt .-% and most preferably between 1.5 and 4% by weight, for example between 2 and 2.5% by weight.
  • the agent is free of polymeric thickeners.
  • one or more dicarboxylic acids and / or salts thereof may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, for example as available under the trade name Sokalan ® DSC is.
  • the use is advantageously carried out in amounts of 0.1 to 8 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1.3 to 6 wt .-% and particularly preferably 2 to 4 wt .-%.
  • a change in the dicarboxylic acid (salt) content can - especially in amounts above 2 wt .-% - contribute to a clear solution of the ingredients. Also, within certain limits, influencing the viscosity of the mixture by this means is possible. Furthermore, this component affects the solubility of the mixture. This component is particularly preferably used at high surfactant contents, in particular at surfactant contents above 30 wt.%.
  • the agent according to the invention is preferably free from dicarboxylic acid (salts).
  • auxiliaries and additives in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ® AGS, or mixtures comprising, for example, the Euperlane ®) SRP (soil repellent polymers), PEG-terephthalate, dyes, bleaching agents (eg hydrogen peroxide), corrosion inhibitors, preservatives (for example, the technical also known as Bronopol 2-bromo-2-nitropropane-1,3-diol ( CAS 52-51-7), which is commercially available) as well as skin feel-improving or caring additives (eg dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin example as Myacide ® BT or as Boots Bronopol BT from Boots C, Vitamin E, D-Panthenol, Sericerin, Collagen Partial Hydro
  • proteases eg BLAP (Henkel), Savinase (NOVO), Durazym (NOVO), Maxapemm, etc.
  • amylases eg Fermamyl (NOVO), etc.
  • lipases eg Lipolase (NOVO), etc.
  • Peroxidases gluconases, cellulases, mannases, etc., in amounts of preferably 0.001 to 1.5%, and more preferably less than 0.5%.
  • the pH of the agent according to the invention can be adjusted by means of customary pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide, wherein - in particular with the desired hand tolerance - a range from 4 to 9, preferably 5 to 8, in particular 6 to 7, is preferred.
  • acids such as mineral acids or citric acid
  • alkalis such as sodium or potassium hydroxide
  • the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 3 wt.%, In particular 0, 01 to 2 wt .-%, particularly preferably 0.05 to 1 wt.%, Most preferably 0.1 to 0.5 wt .-%, for example 0.2 wt .-%.
  • buffer substances which are at the same time complexing agents or even chelating agents ( INCI chelating agents).
  • Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate 2 H 2 O and tripotassium citrate H 2 O.
  • the agent of the invention can be prepared by combining the individual components in any order.
  • the order of attachment is not critical to the preparation of the agent.
  • an agent according to the invention in the previously described embodiments, in which the individual constituents of the composition are mixed together.
  • water surfactants, the silyl polyalkoxylates of the formula (I) according to the invention and optionally further of the aforementioned ingredients are stirred together. If perfume and / or dye are used, then their addition to the resulting solution. Subsequently, the pH is adjusted as described above.
  • the starting material used was a polyether polyol which is a 6-arm random poly (ethylene oxide-co-propylene oxide) having an EO / PO ratio of 80/20 and a molecular weight of 12,000 g / mol, obtained by anionic ring-opening polymerization of ethylene oxide and propylene oxide using sorbitol as initiator.
  • the polyether polyol was heated in vacuo with stirring for 1 h at 80 ° C.
  • Voranol CP 1421 from DOW Chemicals was dried in vacuo with stirring for 1 h at 80 ° C.
  • To 2.04 g (0.41 mmol) of the dried polyether polyol was slowly added 317 mg (1.0 equivalents) of (3-isocyanatopropyl) triethoxysilane.
  • the reaction mixture was further stirred under inert gas at 100 ° C for 2 days until the vibration band of the NCO group disappeared upon IR measurement.
  • Voranol 4053 from DOW Chemicals was dried in vacuo with stirring for 1 h at 80 ° C. 209 g (16.9 mmol) of the dried polyether polyol were added to 20.9 mg (0.01%). Dibutyltin dilaurate and 30.3 g (1.0 equivalents) of (3-isocyanatopropyl) triethoxysilane were slowly added. The reaction mixture was further stirred under inert gas at room temperature for 2 days until the NCO band disappeared on IR measurement.
  • the product was obtained, which in each case has a triethoxylsilyl group at the free ends of the polymer arms of the polyether polyol and represents a mixture of a 3-armed and an 8-armed polyalkoxylate in a ratio of about 20/80, as a colorless viscous liquid.
  • compositions E1-E3 according to the invention and, for comparison, the non-inventive agent V1 were prepared.
  • composition V1 E1 E2 E3 (in% by weight) Na-C 12-14 fatty alcohol + 1.3EO sulphate 10 10 10 10 sec. Na C 13-17 alkanesulfonate 1) 16 16 16 16 cocoamidopropyl 5 5 5 5 Silyl polyalkoxylate 2) - 0.1 0.5 5 ethanol 8th 8th 8th 8th Citric acid H 2 O 0.1 0.1 0.1 0.1 Perfume 0.45 0.45 0.45 0.45 water ad 100 ad 100 ad 100 ad 100 ad 100 1) Hostapur ® SAS 60 (Clariant) 2) Silyl polyalkoxylate according to Example 1
  • the silyl polyalkoxylate was first prepared in the form of a solution (composition: 5 g of silyl polyalkoxylate, 2.5 g of water, 2.5 g of acetic acid, ethanol ad 100 g). An appropriate amount of this solution was mixed with the remaining ingredients of the respective E1 to E3 agents.
  • test body wine glasses black glass plates and black porcelain plates were used.
  • the agents to be tested were applied in a quantity of 1 to 2 g on a sponge, and then cleaned with the sponge, the test specimens. After cleaning, the test pieces were rinsed with lukewarm water. Then the time was left to dry the surfaces were measured and the extent of limescale or visors determined visually and each evaluated in relation to the reference value. As a reference value, ware cleaned with the agent V1 was used.
  • the plate was then placed on a scale connected to a computer and from a wetting of the plate with even 0.05 g of rinsing liquor, ie from a lying by 0.05 g above the weight of the dry plate weight, to the complete dryness of the plate, ie until the weight of the dry plate is reached, the computer records the weight of the plate every second.
  • the humidity was by means of of a hygrometer placed immediately next to the scale and was between 35 and 46% relative humidity. For each rinse liquor 6 measurements were carried out. From the average values of 6 measurements in each case, a higher drying speed was obtained for the agent E3 according to the invention, ie a faster drying or a better drying behavior, than for the comparison means V1.
  • the detergent to be tested in application concentration (2 ml solution to 5000 ml of water, 16 ° dH) were dissolved, immersed black plates, left for about 60 s in the 40 ° C warm rinsing and then quickly pulled out of the fleet.
  • the dry process was recorded in time. The drying times were on average about 3 minutes, wherein the formulation of the invention E3 dried much faster than the comparison means V1.
  • the champagne flutes were equipped by means of a pump with the rinsing liquor heated to 45 ° C. The concentration was 0.4 g of detergent per liter of rinse liquor.
  • the tubular spout attached to the chalice of the champagne flute had a diameter of 15 mm and guided the draining rinse liquor over the balance. Temperature and humidity were monitored during measurements with a hygrometer. For each rinse liquor, 10 measurements were made. Averaged over every 10 measurements, the agent E3 according to the invention showed a higher running speed, ie a faster running or a better running behavior, than the comparison means V1.

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EP07857241A 2006-12-05 2007-12-04 Reinigungsmittel für harte oberflächen Not-in-force EP2108037B1 (de)

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DE102007039649A DE102007039649A1 (de) 2006-12-05 2007-08-22 Reinigungsmittel für harte Oberflächen
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US7998918B2 (en) 2011-08-16
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ATE466067T1 (de) 2010-05-15
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WO2008068235A1 (de) 2008-06-12
DE102007039649A1 (de) 2008-06-12

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