EP2336290A1 - Gel-form preparations - Google Patents
Gel-form preparations Download PDFInfo
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- EP2336290A1 EP2336290A1 EP09015484A EP09015484A EP2336290A1 EP 2336290 A1 EP2336290 A1 EP 2336290A1 EP 09015484 A EP09015484 A EP 09015484A EP 09015484 A EP09015484 A EP 09015484A EP 2336290 A1 EP2336290 A1 EP 2336290A1
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- Prior art keywords
- alcohol
- fatty alcohol
- general formula
- surfactants
- alkyl
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
Definitions
- the present application relates to aqueous, gelatinous preparations which contain certain emulsifiers and optionally further ingredients, and which are distinguished by their particular rheological properties, and to the use of such agents as cleaning agents, in particular for sanitary cleaning.
- Sanitary cleaners are generally understood to mean special cleaners which are intended to remove deposits of lime and, if appropriate, urine stones in the sanitary area, in particular in toilets (cf. Römpp, Chemie Lexikon, 9th edition, 1992, p. 3988 ). Furthermore, such agents often still contain fragrances to mask the typical odors of sanitary facilities, or to give the user an impression of freshness and cleanliness.
- Sanitary cleaners therefore contain conventional water-soluble acid for dissolving limescale or urine scale and regularly a surfactant that must be substantially biodegradable according to the legal requirements, but often leaves a non-degradable residue after use.
- Suitable water-soluble acids are, for example, organic acids such as carboxylic acids having 2 to 3 carbon atoms, dicarboxylic acids having 3 to 8 carbon atoms, hydroxycarboxylic acids having 1 to 6 carbon atoms, 1 to 5 hydroxyl groups and 1 to 3 carboxyl groups or mixtures thereof.
- the sanitary cleaners are flushed into the sewer system, where they may act toxic to the local microflora, thereby delaying the degradation of the biomass in the wastewater.
- the known sanitary cleaner are increasingly critically assessed because of the aforementioned toxic effect on the microorganisms of the wastewater and the pollution of the wastewater and groundwater with incompletely degradable substances or with further questionable degradation materials.
- sanitary agents which are also referred to here as Sanitärreiruger, which should show less of a cleaning rather than a deodorizing effect, and accordingly on a higher proportion of perfumes feature.
- These agents are placed, for example, in the toilet to deliver perfumes there continuously or only on contact with water.
- Sanitary cleaners are usually offered in the form of solid blocks, or as a liquid formulation which is applied directly to the surface of the sanitary facilities - preferably a toilet - or which is used with the aid of a metering device (for example a so-called "toilet bowl”).
- the solid or liquid sanitary cleaner is introduced into the metering device, wherein this metering device is then positioned so that it comes into contact with the flushing water of the toilet so that the cleaner is gradually washed out of the metering device and then in the form of a dilute aqueous Solution can unfold its effect.
- such forms are available in which the sanitary cleaner is made up in the form of a viscous gel.
- gel-like agents containing fragrances, surfactants and a coupling agent being selected from polyalkoxyalkanes, celluloses, starch, alginates, diurethanes, gelatin, pectins, oleylamines, alkyldimethyl aminoxiden, stearates, sodium dodecylbenzenesulfonate, agar-agar, gum arabic, locust bean gum , Polyacrylate, polyvinylalcohol and polyvinylpyrrolidone, and the polyalkoxy group of the polyalkoxyalkanes is preferably a polyethoxy, polypropoxy or polybutoxy or even a mixed polyalkoxy group such as a poly (ethoxypropoxy) group, with polyethoxy groups having between 15 and 55 ethoxy groups, preferably between 25 and 45 and more preferably 35 +/- 5 ethoxy groups, are preferred and the viscosity of the
- adhesive sanitary agents which serve for cleaning and fragrancing and surfactants, water, fragrances and adhesion promoters include. After direct application to the sanitary object these Sanitänstoff rinsed only after a large number of rinsing cycles.
- adhesive sanitary agents based on the block copolymers comprising oligo- or polyalkylene oxides or the aryl ethoxylates or alkyl aryl ethoxylates as adhesion promoters are disclosed in US Pat EP 1 318 191 61 described and adhering sanitary agents with bleaches in the DE 10 2004 056 554 A1 ,
- gels generally dimensionally stable, easily deformable, rich in liquids and gases disperse systems of at least two components
- a solid, colloidally divided material with long or highly branched Particles e.g., gelatin, silicic acid, montmorillonite, bentonites, polysaccharides, pectins, specialty polymers such as polyacrylates, and other gelling agents often referred to as thickeners
- a liquid usually water
- gels are not only viscous but also show elastic properties.
- the gels according to the claimed embodiment are so-called "hum gels", since in a suitable vessel they are capable of producing, with external excitation, a frequency of oscillation which can be perceived by the human ear. This is due to the particular elastic properties of the gels according to the invention.
- Brumm gels are in the Römpp Chemielexikon, online edition, version 3.5 dated 27.07.2009 characterized as follows: Optically isotropic, transparent gels which, due to their energy elasticity, can be stimulated by mechanical shocks to produce vibrations in the audible frequency range. This property was first found in special surfactant systems consisting of surfactants, hydrocarbons and water, so-called microemulsion gels (see microemulsion).
- the audible tone ranges from a low hum to a high metallic sound and depends on the gel itself, the size and geometry of the vessel in which the sample is located, and the fill level.
- the time constant at which the oscillation decays is in the range of one second for most samples.
- hum gels are known and are based for example on amphoteric surfactants and selected ethylene oxide / propylene oxide copolymers in the US 3925241 described. It is noteworthy that only when certain surfactants or thickeners are selected in selected amounts with each other, the gels can be characterized as hum-gels.
- Brummgelen For rheological description of Brummgelen usually the gel is mixed by a mechanical pulse into vibrations of different frequency (eg between 1-100 s -1 ) and then determines the resonance curve of the gel. In the present case, this is done in a commercially available rheometer with plate-plate measurement geometry (see below). In the FIG. 1 is a resonance curve for an inventive Brummgel listed.
- Q ⁇ is a parameter that is characteristic of Brummgele, a low viscous damping is a prerequisite for the occurrence of the hum effect.
- the gels of the present invention show (measured at 23 ° C) viscous damping factors in the range of less than 2.50 Pa s and preferably less than 1.80 Pa s.
- the lower limit for Q ⁇ is preferably a value of 0.01 to 0.05 Pa s or 0.10 Pa s. But particularly preferred is the range of 2.20 to 0.10 Pa s and preferably 2.00 to 0.20 Pa s, and in particular the range of 1.80 to 0.25 Pa s, wherein also the range of 1 , 00 to 0.30 may be of particular advantage.
- the gels in the sense of the present application necessarily contain water, an emulsifier and a surfactant as well as optionally further ingredients, such as emollients and possibly also auxiliaries and additives.
- the gels contain as component b) mandatory emulsifiers, which may preferably be selected from the group of alkoxylated fatty alcohols and esters of hydroxycarboxylic acids and preferably the esters of hydroxycarboxylic acids with alkoxylated fatty alcohols.
- Alkoxylated fatty alcohols of the general formula (I) follow the general formula R- (AO) n -H (I) in which R is a linear, branched, saturated or unsaturated alkyl or alkenyl radical having 12 to 22 C atoms, AO is the groups C 2 H 4 O and / or C 3 H 6 O and the subscript n is a number from 1 to 45, and preferably from 5 to 35.
- Typical examples are also the adducts of on average 1 to 45, preferably 5 to 40 and especially 10 to 25 moles of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol , Petroselinylalkohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, eg incurred in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
- Preferred are adducts of 10 to 40 moles of ethylene oxide with technical fatty alcohol
- alkoxylated Fatty alcohols preferably ethoxylated
- alkoxides preferably only ethylene oxide
- propoxylates or mixed alkoxylates with ethylene oxide and propylene oxide groups (randomized or blockwise distribution).
- a second, preferred class of emulsifiers are the esters of hydroxycarboxylic acids with alkoxylated fatty alcohols.
- Hydroxycarboxylic acids are organic acids which contain at least one OH group in addition to at least one COOH group in the molecule. They can be present as monohydroxycarboxylic acids with one OH group, with two as di-, or with more than two OH groups as polyhydroxycarboxylic acids. After the position of the OH group to the COOH group, a distinction is made between alpha-, beta-, and gamma-hydroxycarboxylic acids.
- the acids can be saturated or unsaturated (examples: ricinoleic acid).
- Known aromatic hydroxycarboxylic acids are salicylic acid (2-hydroxybenzoic acid) and gallic acid (3,4,5-trihydroxybenzoic acid).
- Preferred hydroxycarboxylic acids in the present invention are alpha-hydroxycarboxylic acids, especially tartaric acid, mandelic acid, lactic acid, malic acid, citric acid and their salts.
- esters of hydroxycarboxylic acids with ethoxylated alcohols are known compounds which follow the formula (II), R 1 - (EO) x -Z (II) in which R 1 is an alkyl radical having 6 to 22 C atoms, preferably having 12 to 14 C atoms, X is an integer from 1 to 20, preferably from 2 to 10, and Z is a hydroxycarboxylic acid radical.
- R 1 is an alkyl radical having 6 to 22 C atoms, preferably having 12 to 14 C atoms
- X is an integer from 1 to 20, preferably from 2 to 10
- Z is a hydroxycarboxylic acid radical.
- Preferred hydroxycarboxylic acids in the present invention as radical Z are alpha-hydroxycarboxylic acids, especially tartaric acid, mandelic acid, lactic acid, malic acid and citric acid.
- Compounds of general formula (II) based on citric acid are particularly preferred here.
- the gels according to the invention contain 5 to 35% by weight, preferably 1 to 15% by weight and more preferably 5 to 10% by weight of alpha-hydroxycarboxylic acids and / or their salts, based on the total weight of the composition.
- Suitable third class of emulsifiers are the alkoxylated, preferably the ethoxylated fatty acid polyol partial or full esters.
- glycerol, neopentyl glycol, trimethylolpropane or ethane, and their oligomers or polymers are understood as polyols.
- the polyols form the basis for esters with fatty acids (linear, branched, saturated or unsaturated) having preferably 6 to 22 carbon atoms. Both full and partial esters or mixtures thereof, of the polyols can be used.
- Preferred polyol is the glycerol.
- Suitable fatty acids are those having 6 to 18 and in particular 10 to 16 carbon atoms.
- the temperature is usually in the range of 110 to 180 ° C, the autogenous pressure can rise to 5 bar. After the required amount of ethylene oxide has been added and the pressure has reached a constant value, it is allowed to react for about 30 minutes before cooling the autoclave, depressurized and neutralized or filtered off the alkaline catalyst, for example by adding lactic acid. The addition of catalyst can be omitted in the ethoxylation, if from the previous transesterification, a sufficient amount of alkali is still present.
- the emulsifiers are present in the gels preferably in amounts of from 5 to 30, in particular from 6 to 25 and particularly preferably from 10 to 20 wt .-%, each based on the total weight of the gels.
- Preferred emollients are the fatty alcohols (iv) and the dialkyl carbonates (ii).
- Preferred gels therefore contain either fatty alcohols or dialkyl carbonates, or mixtures of the two substances.
- Dialkyl carbonates preferably follow the general formula (III)
- R 2 and R 3 independently of one another represent linear or branched, saturated or unsaturated alkyl or alkenyl radicals, which preferably contain between 1 and 32 C atoms.
- Preferred dialkyl carbonates are those in which a radical is a branched alkyl radical which is derived from oxo alcohols or the so-called Guerbet alcohols.
- dialkyl carbonates in which R 2 or R 3 is an alkyl radical derived from a Guerbet alcohol are called Guerbet carbonates.
- Guerbet carbonates which are also at low temperatures of for example -25 ° C as clear, colorless to light-colored liquids and are insensitive to hydrolysis due to the branching in the alkyl chain of R 2 or of R 3 and R 2 under normal conditions.
- the preparation of these particularly preferred Guerbetcarbonate can in a conventional manner by the transesterification of dialkyl carbonates with Guerbet alcohols carried out in the presence of basic catalysts.
- Preferred Guerbet carbonates have a branched alkyl radical R 2 having 12 to 28 carbon atoms.
- both R 2 and R 3 represent a branched alkyl radical of 12 to 28 carbon atoms
- Guerbet carbonates having a spreading capacity between 300 and 650 mm / 10 minutes are particularly advantageous.
- Guerbet carbonates with a spreading capacity between 350 and 600 mm / 10 minutes have excellent performance properties.
- Examples of particularly preferred symmetric Guerbet carbonates are those in which R 2 and R 3 is a branched alkyl chain having 16 carbon atoms (spreadability 550 mm / 10 minutes) or with 20 carbon atoms (spreadability 400 mm / 10 minutes).
- fatty alcohols are to be understood as meaning primary aliphatic alcohols of the formula (IV) R 4 OH (IV) in which R 4 is an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
- Typical examples are caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and the like technical mixtures which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols.
- Preferred are technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel
- the emollients are contained in the gels preferably in amounts of from 1 to 20% by weight and more preferably from 5 to 15% by weight, based in each case on the total weight of the gels.
- the gels may optionally contain surfactants which must be structurally different from components a) and b), nonionic, anionic, cationic or betaine type, alone or in combination. Preference is given to anionic and / or nonionic surfactants.
- anionic surfactants of the preparations according to the invention are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid fatty acid
- alkyl sulfates preference is given in the gels according to the invention to alkyl sulfates, fatty alcohol ether sulfates, alkanesulfonates and alkylsulfosuccinates, particularly preferably the alkyl and / or alkenyl sulfates, and also the alkyl ether sulfates.
- Alkyl and / or alkenyl sulfates which are also frequently referred to as fatty alcohol sulfates, are the sulfation products of primary alcohols which follow the formula (II), R 5 O-SO 3 X (V) in which R 5 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- alkyl sulfates which can be used according to the invention are the sulfation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures obtained by high-pressure hydrogenation of technical methyl ester fractions or aldehydes from the Roelen oxo synthesis.
- the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Particular preference is given to alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
- ether sulfates are known anionic surfactants which are industrially produced by SO 3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxoalcohol polyglycol ethers and subsequent neutralization.
- ether sulfates come into consideration, which follow the formula (VI), R 6 O- (CH 2 CH 2 O) m SO 3 X (VI) in which R 6 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, m is a number from 0 or 1 to 10 and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- Typical examples are the sulfates of adducts of on average 0 or 1 to 10 and especially 1 to 5 moles of ethylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol 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. Particularly preferred is the use of ether sulfates based on adducts of on average 1.5 to 2.5 moles of ethylene oxide to technical C 12/14 - or C 12/18 - Kokosfettalkoholfr hopeen in the form of their sodium and / or magnesium salts.
- nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, optionally partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products). , Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution.
- a preferred class of nonionic surfactants are the alkyl (oligo) glycosides.
- Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow formula (VII), R 7 O- [G] p (VII) where R 7 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.
- the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose.
- the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
- the index number p in the general formula (VII) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
- alkyloligoglycoside is analytically determined mathematical size, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred.
- the alkyl or alkenyl radical R 7 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms.
- Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis.
- the alkyl or alkenyl radical R 7 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of 1 to 3.
- gels are selected which contain alky (oligo) glycosides as nonionic surfactants, preferably in combination with at least one emulsifier b) selected from a compound of general formula (I).
- gels containing as emulsifier partial ester of a hydroxycarboxylic acid with an alkoxylated fatty alcohol together with an alkoxylated fatty alcohol according to the general formula (I), but optionally in combination with an alkyl (oligo) glycoside as nonionic surfactant.
- cationic surfactants are quaternary ammonium compounds and ester quats, especially quaternized fatty acid trialkanolamine ester salts.
- Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.
- surfactants are present in the gels, they are used in amounts of from 1 to 25% by weight and preferably from 10 to 20% by weight, based in each case on the total weight of the gels. It is possible to use only one class of surfactants, preferably anionic or nonionic surfactants, or mixtures of surfactants, either from one class or from several classes among themselves.
- Paraffins are preferred hydrocarbons in the context of the present application.
- the paraffins are preferably used in amounts of from 1 to 20% by weight and preferably from 1 to 10% by weight and in particular from 4 to 8% by weight. Different qualities of paraffins can be used. However, paraffins which are liquid at room temperature are preferably used. Furthermore, the use of two or more different hydrocarbons, preferably a paraffin oil and gasoline is preferred.
- paraffins are preferably used in those gels which have anionic surfactants as surfactant component, in which case those formulations which contain fatty alcohol sulfates may be advantageous.
- hydrocarbons in such gel formulations containing as emulsifier fatty alcohol ethoxylates of the general formula (I).
- emulsifier fatty alcohol ethoxylates of the general formula (I).
- Preferred representatives of these alkoxylates then follow the general formula (I), where n here is in the range from 1 to 10 and preferably 1 to 6 or 1 to 5.
- the gels may also contain other auxiliaries and additives. These include perfumes, biocides, pH regulants, dyes, preservatives, non-aqueous solvents, defoamers, thickeners, and / or disinfectants. Strong acids, in particular inorganic acids such as HCl or sulfuric acid are also suitable additives. However, it may also be preferable to completely dispense with the presence of acids in the gelled agents.
- fragrances which are solid but preferably liquid, are partially complex mixtures of various individual chemical compounds, the so-called fragrances.
- the fragrances can be selected from a wide variety of chemical classes. It is possible to distinguish between alkali-stable and less alkali-stable fragrances.
- Alkali-stable fragrances are preferred and can be used here, for example linalool, geraniol, acetophenone, lilial, geranonitrile, dihydromyrcenol, o-tert-butylcyclohexyl acetate, anisaldehyde, tetrahydrolinalool, citronellol, cyclohexyl salicylate, phenylethyl alcohol, benzophenone, rose oxide, methyl benzoate, alpha-hexyl cinnamaldehyde; the less alkali-stable fragrances include vetiveryl acetate, delta-dodecalactone, allylamyl glycolate, hydroxycitronellal, benzyl acetate, amyl butyrate.
- fragrances are acetophenone, acetyleugenol, alum root oil, 1-allyl-2,5-dimethoxy-3,4- (methylenedioxy) benzene, 1-allyl-3-methoxy-4,5-methylene-dioxy-benzene, 1 Allyl-3,4,5-trimethoxybenzene, allyl isothiocyanate (allyl mustard), allyl ionone, ethyl formate, alpha-amylcinnamic aldehyde, anethole, anisaldehyde, apiol (parsley apiol), alpha-asarone, beta-asarone, ascaridol, Atlanton, valerian oil, benzaldehyde, benzylacetone, Benzyl alcohol (“phenylmethanol”), bergamotenal, bergamot oil, alpha-bisabolol, bitter almond oil cyanogen-free, cis-3
- the content of fragrances (based on the total weight of the gels) in the gels according to the invention is between 0.01 and 25% by weight, preferably 0.01 to 15% by weight, with contents between 1.0 and 10% by weight. and in particular 1.5 to 6 wt .-% are preferred.
- the aqueous gels of the present invention may have a pH in the range of from 2 to 12, preferably from 3 to 10.5, and more preferably from 3.5 to 8, wherein the pH may be adjusted by conventional per se or acids.
- acids preferably hydroxycarboxylic acids, e.g. the citric acid used.
- gels which contains 10 to 20 wt .-% of ethoxylated fatty alcohols according to the general formula (I), wherein n is a number from 25 to 35, 15 to 25 wt .-% of further Emulsifiers b) selected from the group of partial esters of a hydroxycarboxylic acid with an alkoxylated fatty alcohol and / or the ethoxylated fatty acid polyol partial or full esters; optionally 1 to 29 wt .-% of an emollient according to the above description and the remainder to 100 wt .-% water and optionally auxiliaries and additives.
- Emulsifiers b) selected from the group of partial esters of a hydroxycarboxylic acid with an alkoxylated fatty alcohol and / or the ethoxylated fatty acid polyol partial or full esters; optionally 1 to 29 wt .-% of an emollient according to the above description and the remainder to 100
- such gels are also preferably 10 to 25% by weight of an anionic surfactant, preferably a fatty alcohol sulfate; 10 to 20 wt .-% of an ethoxylated fatty alcohol according to the general formula (I) with n from 1 to 10; 1 to 10% by weight of an emollient i) to v) as described above; 10 to 20 wt .-% of a hydrocarbon and the balance to 100 wt .-% water and optionally auxiliaries and additives.
- an anionic surfactant preferably a fatty alcohol sulfate
- 10 to 20 wt .-% of a hydrocarbon and the balance to 100 wt .-% water and optionally auxiliaries and additives.
- the preparation of the gels is carried out by combining the different components, wherein both the known hot and cold methods can be used. Hot processes become particularly necessary if ingredients of the recipe are solid at room temperature; These must then first be melted and then mixed with the other ingredients.
- the gels according to the invention are particularly suitable as sanitary cleaners, preferably as sanitary cleaners set the fragrances free for toilets. They are easily self-adhesive and do not dissolve too quickly on contact with, in particular, cold water (temperature ⁇ 20 ° C and especially ⁇ 14 ° C).
- the preparation was carried out by preparing a mixture of the ingredients without the perfume at room temperature. Thereafter, the mixture was heated. The water was brought to about 85 ° C and then the perfume is cold weighed into the hot mixture and stirred. Thereafter, the water was added warm and also stirred.
- a rinsing test was carried out as follows: Approx. 5g of the sample was spread on a tile and painted into a uniform lump. A water hose was attached to a tripod and narrowed with a pinch cock to increase the power of the jet. The water jet (temperature of the water about 18 to 20 ° C) was set so that it comes up just over the point, the faucet was opened by about 90 °. The time was then measured until the gel sample was rinsed off.
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Abstract
Description
Gegenstand der vorliegenden Anmeldung sind wässerige, gelförmige Zubereitungen, die bestimmte Emulgatoren und ggf. weitere Inhaltsstoffe enthalten, und die sich durch ihre besonderen rheologischen Eigenschaften auszeichnen, und die Verwendung derartiger Mittel als Reinigungsmittel, insbesondere für die Sanitärreinigung.The present application relates to aqueous, gelatinous preparations which contain certain emulsifiers and optionally further ingredients, and which are distinguished by their particular rheological properties, and to the use of such agents as cleaning agents, in particular for sanitary cleaning.
Unter Sanitärreinigem versteht man generell spezielle Reinigungsmittel, die im Sanitärbereich, insbesondere in Toiletten, Ablagerungen von Kalk- und gegebenenfalls Urinsteinen beseitigen sollen (vgl.
Sanitärreiniger enthalten daher übliche wasserlösliche Säure zum Lösen von Kalkablagerungen bzw. Urinstein und regelmäßig ein Tensid, das nach den gesetzlichen Vorschriften im wesentlichen biologisch abbaubar sein muss, jedoch häufig nach der Anwendung einen nicht abbaubaren Rest belässt. Geeignete wasserlösliche Säuren sind beispielsweise organische Säuren, wie Carbonsäuren mit 2 bis 3 Kohlenstoffatomen, Dicarbonsäuren mit 3 bis 8 Kohlenstoffatomen, Hydroxycarbonsäuren mit 1 bis 6 Kohlenstoffatomen, 1 bis 5 Hydroxylgruppen und 1 bis 3 Carboxylgruppen oder deren Gemische. Nach der Benutzung z. B. im Toilettenbecken werden die Sanitärreiniger in das Abwassersystem gespült, wo sie unter Umständen auf die dortige Mikroflora toxisch einwirken und dadurch den Abbau der Biomasse im Abwasser verzögern. Trotz guter Reinigungswirkung werden die bekannten Sanitärreiniger wegen der angesprochenen toxischen Wirkung auf die Mikroorganismen des Abwassers und der Belastung des Abwassers und des Grundwassers mit unvollsttindig abbaubaren Stoffen bzw. mit weiterhin bedenklichen Abbaustoffen zunehmend kritisch beurteilt.Sanitary cleaners therefore contain conventional water-soluble acid for dissolving limescale or urine scale and regularly a surfactant that must be substantially biodegradable according to the legal requirements, but often leaves a non-degradable residue after use. Suitable water-soluble acids are, for example, organic acids such as carboxylic acids having 2 to 3 carbon atoms, dicarboxylic acids having 3 to 8 carbon atoms, hydroxycarboxylic acids having 1 to 6 carbon atoms, 1 to 5 hydroxyl groups and 1 to 3 carboxyl groups or mixtures thereof. After using z. B. in the toilet bowl, the sanitary cleaners are flushed into the sewer system, where they may act toxic to the local microflora, thereby delaying the degradation of the biomass in the wastewater. Despite good cleaning effect, the known sanitary cleaner are increasingly critically assessed because of the aforementioned toxic effect on the microorganisms of the wastewater and the pollution of the wastewater and groundwater with incompletely degradable substances or with further questionable degradation materials.
Es gibt aber auch Sanitärmittel, die hier ebenfalls als Sanitärreiruger bezeichnet werden, die weniger eine Reinigungs- als vielmehr eine desodorierende Wirkung zeigen sollen, und dementsprechend über einen höheren Anteil an Duftstoffen verfügen. Diese Mittel werden z.B. in der Toilette platzier, um dort kontinuierlich oder nur bei Kontakt mit Wasser Duftstoffe abzugeben.But there are also sanitary agents, which are also referred to here as Sanitärreiruger, which should show less of a cleaning rather than a deodorizing effect, and accordingly on a higher proportion of perfumes feature. These agents are placed, for example, in the toilet to deliver perfumes there continuously or only on contact with water.
Sanitärreiniger werden üblicherweise in Form fester Blöcke angeboten, oder als flüssige Formulierung, die direkt auf die Oberfläche der Sanitäranlagen - vorzugsweise einer Toilette - aufgebracht wird, oder die mit Hilfe einer Dosiervorrichtung (z.B. einem so genannten "WC-Körbchen") verwendet wird. Der feste oder flüssige Sanitärreiniger wird dazu in die Dosiervorrichtung eingebracht, wobei diese Dosiereinrichtung dann so positioniert wird, dass sie mit dem Spülwasser der Toilette so in Kontakt kommt, das der Reiniger nach und nach aus der Dosiereinrichtung herausgespült wird und dann in Form einer verdünnten wässerigen Lösung seine Wirkung entfalten kann. Dabei sind auch solche Angebotsformen erhältlich, bei denen der Sanitärreiniger in Form eines viskosen Gels konfektioniert wird. Diese Gele haben den Vorteil, dass sie sich schneller auflösen als feste Angebotsformen, ohne dass es zu einer unerwünschten Überdosierung im Einsatz kommt. Es werden neuerdings auch Gel-förmige Produkte angeboten, die eine gewisse Haftwirkung auf harten Oberflächen zeigen. Derartige selbsthaftende Gele sollen dann ohne Dosiervorrichtung auskommen, was aus Sicht der Benutzer eine Verbesserung darstellt.Sanitary cleaners are usually offered in the form of solid blocks, or as a liquid formulation which is applied directly to the surface of the sanitary facilities - preferably a toilet - or which is used with the aid of a metering device (for example a so-called "toilet bowl"). The solid or liquid sanitary cleaner is introduced into the metering device, wherein this metering device is then positioned so that it comes into contact with the flushing water of the toilet so that the cleaner is gradually washed out of the metering device and then in the form of a dilute aqueous Solution can unfold its effect. In this case, such forms are available in which the sanitary cleaner is made up in the form of a viscous gel. These gels have the advantage that they dissolve faster than solid forms of supply, without causing an undesirable overdose in use. Recently, there are also gel-shaped products offered that show a certain adhesion to hard surfaces. Such self-adhesive gels should then do without dosing, which represents an improvement from the user's point of view.
In der
Aus der
In der Praxis besteht aber nach wie vor ein Bedarf derartigen, haftenden Sanitärmittel in ihren Eigenschaften zu verbessern, insbesondere was das Haftvermögen an harten Oberflächen angeht. Außerdem muss das Auflösevermögen der Gele in Wasser weiter optimiert werden. Hier ist zu beachten, dass in einer Toilettenspülung üblicherweise nur kaltes Wasser (d.h. kleiner als 20 °C, teilweise bis zu 6 °C oder 4 °c) verwendet wird, was zu verzögertem Auflösen von Tensiden bzw. dem gesamtem Mittel führten kann. Außerdem variiert die Wassermenge je nach Anwender und somit muss das Sanitärmittel sowohl bei großen als auch bei kleinen Wassermengen zuverlässig und kontrolliert gelöst werden, ohne dass dadurch die Haftung des Gels an der harten Oberfläche nachteilig beeinflusst wird.In practice, however, there is still a need to improve such properties of adherent sanitary agents, particularly as regards adhesion to hard surfaces. In addition, the dissolving power of the gels in water must be further optimized. It should be noted here that in a toilet flush, usually only cold water (i.e., less than 20 ° C, sometimes up to 6 ° C or 4 ° C) is used, which may result in delayed dissolution of surfactants or the total agent. In addition, the amount of water varies depending on the user and thus the sanitary agent must be reliably and controlled solved both large and small amounts of water, without adversely affecting the adhesion of the gel to the hard surface.
Es wurde gefunden, dass Gele mit bestimmten rheologischen Eigenschaften diese Nachteile nicht mehr aufweisen.It has been found that gels with certain rheological properties no longer have these disadvantages.
Ein erster Gegenstand der vorliegenden Anmeldung betrifft daher ein gelförmiges Mittel, enthaltend bezogen auf das Gesamtgewicht des Mittels
- a) 45 bis 90 Gew.-% Wasser;
- b) 5 bis 35 Gew.-% Emulgatoren und
- c) 1 bis 25 Gew.-% Tenside sowie
- d) optional weitere Hilfs- und Zusatzstoffe
- a) 45 to 90% by weight of water;
- b) 5 to 35 wt .-% emulsifiers and
- c) 1 to 25 wt .-% surfactants and
- d) optionally further auxiliaries and additives
Als Gele werden generell formbeständige, leicht deformierbare, an Flüssigkeiten und Gasen reiche disperse Systeme aus mindestens zwei Komponenten bezeichnet, die zumeist aus einem festen, kolloidzerteilten Stoff mit langen oder stark verzweigten Teilchen (z. B. Gelatine, Kieselsäure, Montmorillonit, Bentonite, Polysaccharide, Pektine, spezielle Polymere, wie z. B. Polyacrylate, und andere, oft als Verdickungsmittel bezeichnete Geliermittel) und einer Flüssigkeit (meist Wasser) als Dispersionsmittel bestehen. Gele sind im Gegensatz zu Flüssigkeiten nicht nur viskos sondern zeigen auch elastische Eigenschaften. Bei den Gelen gemäß der anspruchsgemäßen Ausfiihrungsform handelt es sich um so genannte "Brumm-Gele", da sie in einem geeigneten Gefäß in der Lage sind, bei externen Anregung eine Schwingungsfrequenz zu erzeugen, die vom menschlichen Ohr wahrgenommen werden kann. Dies begründet sich in den besonderen elastischen Eigenschaften der erfindungsgemäßen Gele.As gels generally dimensionally stable, easily deformable, rich in liquids and gases disperse systems of at least two components are referred to, which usually consists of a solid, colloidally divided material with long or highly branched Particles (e.g., gelatin, silicic acid, montmorillonite, bentonites, polysaccharides, pectins, specialty polymers such as polyacrylates, and other gelling agents often referred to as thickeners) and a liquid (usually water) as a dispersing agent. Unlike liquids, gels are not only viscous but also show elastic properties. The gels according to the claimed embodiment are so-called "hum gels", since in a suitable vessel they are capable of producing, with external excitation, a frequency of oscillation which can be perceived by the human ear. This is due to the particular elastic properties of the gels according to the invention.
Brumm-Gele werden im
Solche Brumm-Gele sind bekannt und werden beispielsweise auf Basis von amphotheren Tensiden und ausgewählten Ethylenoxid/Propylenoxid-Copolymeren in der
Zur rheologischen Beschreibung von Brummgelen wird üblicherweise das Gel durch einen mechanischen Impuls in Schwingungen unterschiedlicher Frequenz (z.B. zwischen 1-100 s-1) versetzt und dann die Resonanzkurve des Gels bestimmt. Im vorliegenden Falle geschieht dies in einem kommerziell erhältlichen Rheometer mit Platte-Platte Messgeometrie (s. u.). In der
Dies gilt auch für die Gele der vorliegenden Erfindung. Mathematisch lässt sich das System als Torsionspendel beschreiben, für das die Bewegungsgleichung
gilt, wobei
- ϕ Auslenkungswinkel
- M0 = Amplitude des Torsionsdrehmomentes
- D = Torsions-Federkonstante
- ω = Schwingungsfrequenz
- I = Trägheitsmoment
- k = Dämpfungskonstante
applies, where
- φ deflection angle
- M 0 = amplitude of the torsion torque
- D = torsion spring constant
- ω = oscillation frequency
- I = moment of inertia
- k = damping constant
Als Lösung der obigen Differentialgleichung erhält man für die Auslenkung A(ω)
In der
wobei h das Spalthöhe und r den Radius bedeuten. Qη ist ein für Brummgele charakteristischer Parameter, eine geringe viskose Dämpfung ist Voraussetzung für das Auftreten des Brummeffektes. Die Gele der vorliegenden Erfindung zeigen (gemessen bei 23 °C) viskose Dämpfungsfaktoren im Bereich kleiner 2,50 Pa s und vorzugsweise kleiner 1,80 Pa s. Als Untergrenze für Qη ist vorzugsweise ein Wert von 0,01 bis 0,05 Pa s oder 0,10 Pa s anzusehen. Besonders bevorzugt ist aber der Bereich von 2,20 bis 0,10 Pa s und vorzugsweise 2,00 bis 0,20 Pa s, und hier insbesondere der Bereich von 1,80 bis 0,25 Pa s, wobei auch der Bereich von 1,00 bis 0,30 von besonderer vorteilhafter Bedeutung sein kann.In the
where h is the gap height and r is the radius. Q η is a parameter that is characteristic of Brummgele, a low viscous damping is a prerequisite for the occurrence of the hum effect. The gels of the present invention show (measured at 23 ° C) viscous damping factors in the range of less than 2.50 Pa s and preferably less than 1.80 Pa s. The lower limit for Q η is preferably a value of 0.01 to 0.05 Pa s or 0.10 Pa s. But particularly preferred is the range of 2.20 to 0.10 Pa s and preferably 2.00 to 0.20 Pa s, and in particular the range of 1.80 to 0.25 Pa s, wherein also the range of 1 , 00 to 0.30 may be of particular advantage.
Die Gele im Sinne der vorliegenden Anmeldung enthalten als Basis zwingend Wasser, einen Emulgator und ein Tensid sowie optional weitere Inhaltsstoffe, wie Emollients und ggf. noch Hilfs- und Zusatzstoffe.The gels in the sense of the present application necessarily contain water, an emulsifier and a surfactant as well as optionally further ingredients, such as emollients and possibly also auxiliaries and additives.
Die Gele enthalten als Komponente b) zwingend Emulgatoren, die vorzugsweise ausgewählt sein können aus der Gruppe der alkoxylierten Fettalkohole und von Estern von Hydroxycarbonsäuren und vorzugsweise der Ester von Hydroxycarbonsäuren mit alkoxylierten Fettalkoholen.The gels contain as component b) mandatory emulsifiers, which may preferably be selected from the group of alkoxylated fatty alcohols and esters of hydroxycarboxylic acids and preferably the esters of hydroxycarboxylic acids with alkoxylated fatty alcohols.
Alkoxylierten Fettalkohole der allgemeinen Formel (I) folgen der allgemeinen Formel
R-(AO)n-H (I)
in der R für einen linearen, verzweigten, gesättigten oder ungesättigten Alkyl- oder Alkenylrest mit 12 bis 22 C-Atomen steht, AO für die Gruppen C2H4O und/oder C3H6O steht und der Index n einen Zahl von 1 bis 45, und vorzugsweise von 5 bis 35 bedeutet.Alkoxylated fatty alcohols of the general formula (I) follow the general formula
R- (AO) n -H (I)
in which R is a linear, branched, saturated or unsaturated alkyl or alkenyl radical having 12 to 22 C atoms, AO is the groups C 2 H 4 O and / or C 3 H 6 O and the subscript n is a number from 1 to 45, and preferably from 5 to 35.
Typische Beispiele sind weiterhin die Addukte von durchschnittlich 1 bis 45, vorzugsweise 5 bis 40 und insbesondere 10 bis 25 Mol an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Bevorzugt sind Addukte von 10 bis 40 Mol Ethylenoxid an technische Fettalkohole mit 12 bis 18 Kohlenstoffatomen, wie beispielsweise Kokos-, Palm-, Palmkern- oder Talgfettalkohol.Typical examples are also the adducts of on average 1 to 45, preferably 5 to 40 and especially 10 to 25 moles of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol , Petroselinylalkohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, eg incurred in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Preferred are adducts of 10 to 40 moles of ethylene oxide with technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol.
Auch der Bereich von 6 bis 20 Teilen AO kann bevorzugt sein, ebenso wie der Bereich von 5 bis 15 oder 5 bis 10. Weiterhin bevorzugt sind alkoxylierte Fettalkohole (vorzugsweise ethoxyliert), die 1 bis 10 Mol und vorzugsweise 2 bis 6 Mol Alkoxide, vorzugsweise nur Ethylenoxid enthalten.Also, the range of 6 to 20 parts of AO may be preferable, as well as the range of 5 to 15 or 5 to 10. Further preferred are alkoxylated Fatty alcohols (preferably ethoxylated) containing from 1 to 10 moles and preferably from 2 to 6 moles of alkoxides, preferably only ethylene oxide.
Neben den Ethoxylaten können auch Propoxylate oder gemischte Alkoxylate mit Ethylenoxid und Propylenoxidgruppen (randomisiert oder blockweise Verteilung) eingesetzt werden.In addition to the ethoxylates, it is also possible to use propoxylates or mixed alkoxylates with ethylene oxide and propylene oxide groups (randomized or blockwise distribution).
Ein zweite, bevorzugte Klasse von Emulgatoren sind die Ester von Hydroxycarbonsäuren mit alkoxylierten Fettalkoholen. Hydroxycarbonsäuren sind organische Säuren, die neben mindestens einer COOH-Gruppe im Molekül mindestens eine OH-Gruppe enthalten. Sie können als Monohydroxycarbonsäuren mit einer OH-Gruppe vorliegen, mit zwei als Di-, oder mit mehr als zwei OH-Gruppen als Polyhydroxycarbonsäuren vorliegen. Nach der Stellung der OH-Gruppe zur COOH-Gruppe unterscheidet man alpha-, beta-, und gamma-Hydroxycarbonsäuren. Die Säuren können gesättigt oder ungesättigt (Beisp.: Ricinolsäure) vorkommen. Bekannte aromatische Hydroxycarbonsäuren sind die Salicylsäure (2-Hydroxybenzoesäure) und die Gallussäure (3,4,5-Trihydroxybenzoesäure). In der vorliegenden Erfindung bevorzugte Hydroxycarbonsäuren, stellen alpha-Hydroxycarbonsäuren, darunter insbesondere die Weinsäure, Mandelsäure, Milchsäure, Äpfelsäure, Citronensäure und deren Salze.A second, preferred class of emulsifiers are the esters of hydroxycarboxylic acids with alkoxylated fatty alcohols. Hydroxycarboxylic acids are organic acids which contain at least one OH group in addition to at least one COOH group in the molecule. They can be present as monohydroxycarboxylic acids with one OH group, with two as di-, or with more than two OH groups as polyhydroxycarboxylic acids. After the position of the OH group to the COOH group, a distinction is made between alpha-, beta-, and gamma-hydroxycarboxylic acids. The acids can be saturated or unsaturated (examples: ricinoleic acid). Known aromatic hydroxycarboxylic acids are salicylic acid (2-hydroxybenzoic acid) and gallic acid (3,4,5-trihydroxybenzoic acid). Preferred hydroxycarboxylic acids in the present invention are alpha-hydroxycarboxylic acids, especially tartaric acid, mandelic acid, lactic acid, malic acid, citric acid and their salts.
Die Ester der Hydroxycarbonsäuren mit ethoxylierten Alkoholen stellen bekannte Verbindungen dar, die der Formel (II) folgen,
R1-(EO)x-Z (II)
in der R1 für einen Alkylrest mit 6 bis 22 C-Atomen, bevorzugt mit 12 bis 14 C-Atomen, X für einen ganzzahligen Wert von 1 bis 20, bevorzugt von 2 bis 10 und Z für einen Hydroxycarbonsäurerest steht. In der vorliegenden Erfindung bevorzugte Hydroxycarbonsäuren als Rest Z, stellen alpha-Hydroxycarbonsäuren, darunter insbesondere die Weinsäure, Mandelsäure, Milchsäure, Äpfelsäure und die Citronensäure dar. Verbindungen der allgemeinen Formel (II) basierend auf der Citronensäure sind hier besonders bevorzugt.The esters of hydroxycarboxylic acids with ethoxylated alcohols are known compounds which follow the formula (II),
R 1 - (EO) x -Z (II)
in which R 1 is an alkyl radical having 6 to 22 C atoms, preferably having 12 to 14 C atoms, X is an integer from 1 to 20, preferably from 2 to 10, and Z is a hydroxycarboxylic acid radical. Preferred hydroxycarboxylic acids in the present invention as radical Z are alpha-hydroxycarboxylic acids, especially tartaric acid, mandelic acid, lactic acid, malic acid and citric acid. Compounds of general formula (II) based on citric acid are particularly preferred here.
Auch Mischungen dieser ethoxylierten Hydroxycarbonsäuren sind geeignet und bevorzugt.Mixtures of these ethoxylated hydroxycarboxylic acids are also suitable and preferred.
Die erfindungsgemäßen Gele enthalten 5 bis 35 Gew. %, vorzugsweise 1 bis 15 Gew.- % und besonders bevorzugt 5 bis 10 Gew. % alpha-Hydroxycarbonsäuren und/oder deren Salze bezogen auf das Gesamtgewicht des Mittels.The gels according to the invention contain 5 to 35% by weight, preferably 1 to 15% by weight and more preferably 5 to 10% by weight of alpha-hydroxycarboxylic acids and / or their salts, based on the total weight of the composition.
Als dritte Klasse von Emulgatoren kommen die alkoxylierten, vorzugsweise die ethoxylierten Fettsäurepolyolpartial- oder Vollester in Betracht. Als Polyole werden insbesondere Glycerin, Neopentylglykol, Trimethylolpropan oder -ethan, sowie deren oligomere oder Polymere verstanden. Die Polyole bilden die Grundlage für Ester mit Fettsäuren (linear, verzweigt, gesättigt oder ungesättigt) mit vorzugsweise 6 bis 22 Kohlenstoffatomen. Dabei können sowohl Voll- als auch Partialester oder Mischungen davon, der Polyole Verwendung finden. Bevorzugtes Polyol ist das Glycerin. Als Fettsäuren kommen solche mit 6 bis 18 und insbesondere 10 bis 16 Kohlenstoffatomen in Frage. Bei diesen Ethoxylierungsprodukten von Partialglyceriden handelt es sich bekannte Stoffe, wie sie beispielsweise auch in der deutschen Patentschrift
Die Emulgatoren kommen in den Gelen vorzugsweise in Mengen von 5 bis 30, insbesondere von 6 bis 25 und besonders bevorzugt von 10 bis 20 Gew.-%, jeweils bezogen auf das Gesamtgewicht der Gele vor.The emulsifiers are present in the gels preferably in amounts of from 5 to 30, in particular from 6 to 25 and particularly preferably from 10 to 20 wt .-%, each based on the total weight of the gels.
Als Emollients kommen im Sinne der vorliegenden technischen Lehre insbesondere in Frage:
- (i) Dialkylether, mit 8 bis 32 C-Atomen;
- (ii) der Dialkylcarbonate mit 8 bis 32 C-Atomen;
- (iii) Estern von Monocarbonsäuren mit einwertigen Fettalkoholen;
- (iv) Fettalkohole mit 8 bis 32 C-Atomen,
- (v) oder Mischungen daraus.
- (i) dialkyl ethers having 8 to 32 C atoms;
- (ii) the dialkyl carbonates having 8 to 32 carbon atoms;
- (iii) esters of monocarboxylic acids with monohydric fatty alcohols;
- (iv) fatty alcohols having 8 to 32 C atoms,
- (v) or mixtures thereof.
Als bevorzugte Emollients sind die Fettalkohole (iv) und die Dialkylcarbonate (ii) anzusehen. Bevorzugte Gele enthalten daher entweder Fettalkohole oder Dialkylcarbonate, oder Mischungen der beiden Substanzen.Preferred emollients are the fatty alcohols (iv) and the dialkyl carbonates (ii). Preferred gels therefore contain either fatty alcohols or dialkyl carbonates, or mixtures of the two substances.
Dialkylcarbonate folgen vorzugsweise der allgemeinen Formel (III)
Wobei R2 und R3 unabhängig voneinander lineare oder verzeigte, gesättigte oder ungesättigte alkyl- bzw. Alkenylreste darstellen, die vorzugsweise zwischen 1 und 32 C-Atomen enthalten. Bevorzugte Dialkylcarbonate sind solche, in denen ein Rest für einen verzweigten Alkylrest steht, der sich von Oxoalkoholen oder den so genannten Guerbetalkoholen ableitet. Im Rahmen dieser Offenbarung werden Dialkylcarbonate, in denen ein Rest R2 oder R3 einen Alkylrest darstellt, der sich von einem Guerbetalkohol ableitet, Guerbetcarbonate genannt. Diese Guerbetcarbonate, die auch bei tiefen Temperaturen von beispielsweise -25 °C als klare, farblose bis hellfarbige Flüssigkeiten vorliegen und aufgrund der Verzweigung in der Alkylkette von R2 oder von R3 und R2 unter normalen Bedingungen unempfindlich gegen Hydrolyse sind. Die Herstellung dieser insbesondere bevorzugten Guerbetcarbonate kann in an sich bekannter Weise durch die Umesterung von Dialkylcarbonaten mit Guerbetalkoholen in Gegenwart basischer Katalysatoren durchgeführt. Bevorzugte Guerbetcarbonate weisen einen verzweigten Alkylrest R2 mit 12 bis 28 Kohlenstoffatomen auf. Insbesondere sind symmetrische und asymmetrische Guerbetcarbonate bevorzugt, in denen sowohl R2 als auch R3 einen verzweigten Alkylrest mit 12 bis 28 Kohlenstoffatomen darstellen, wobei Guerbetcarbonate, die ein Spreitvermögen zwischen 300 und 650 mm/10 Minuten (gemessen nach der Methode von U. Zeidler, Fette, Seifen, Anstrichmittel 87, 403 ff. (1985)) besonders vorteilhaft sind. Vorzügliche anwendungstechnische Eigenschaften besitzen Guerbetcarbonate mit einem Spreitvermögen zwischen 350 und 600 mm/10 Minuten. Beispiele für besonders bevorzugte symmetrische Guerbetcarbonate sind solche, in denen R2 und R3 für eine verzweigte Alkylkette mit 16 Kohlenstoffatomen (Spreitvermögen 550 mm/10 Minuten) oder mit 20 Kohlenstoffatomen (Spreitvermögen 400 mm/10 Minuten) steht.Wherein R 2 and R 3 independently of one another represent linear or branched, saturated or unsaturated alkyl or alkenyl radicals, which preferably contain between 1 and 32 C atoms. Preferred dialkyl carbonates are those in which a radical is a branched alkyl radical which is derived from oxo alcohols or the so-called Guerbet alcohols. For the purposes of this disclosure, dialkyl carbonates in which R 2 or R 3 is an alkyl radical derived from a Guerbet alcohol are called Guerbet carbonates. These Guerbet carbonates, which are also at low temperatures of for example -25 ° C as clear, colorless to light-colored liquids and are insensitive to hydrolysis due to the branching in the alkyl chain of R 2 or of R 3 and R 2 under normal conditions. The preparation of these particularly preferred Guerbetcarbonate can in a conventional manner by the transesterification of dialkyl carbonates with Guerbet alcohols carried out in the presence of basic catalysts. Preferred Guerbet carbonates have a branched alkyl radical R 2 having 12 to 28 carbon atoms. In particular, symmetric and asymmetric Guerbet carbonates are preferred in which both R 2 and R 3 represent a branched alkyl radical of 12 to 28 carbon atoms, Guerbet carbonates having a spreading capacity between 300 and 650 mm / 10 minutes (measured by the method of U. Zeidler , Fats, soaps, paints 87, 403 ff. (1985)) are particularly advantageous. Guerbet carbonates with a spreading capacity between 350 and 600 mm / 10 minutes have excellent performance properties. Examples of particularly preferred symmetric Guerbet carbonates are those in which R 2 and R 3 is a branched alkyl chain having 16 carbon atoms (spreadability 550 mm / 10 minutes) or with 20 carbon atoms (spreadability 400 mm / 10 minutes).
Ebenfalls geeignet sind Fettalkohole. Unter Fettalkoholen sind primäre aliphatische Alkohole der Formel (IV) zu verstehen,
R4OH (IV)
in der R4 für einen aliphatischen, linearen oder verzweigten Kohlenwasserstoffrest mit 6 bis 22 Kohlenstoffatomen und 0 und/oder 1, 2 oder 3 Doppelbindungen steht. Typische Beispiele sind Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelen'schen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Bevorzugt sind technische Fettalkohole mit 12 bis 18 Kohlenstoffatomen, wie beispielsweise Kokos-, Palm-, Palmkern- oder Talgfettalkohol.Also suitable are fatty alcohols. Fatty alcohols are to be understood as meaning primary aliphatic alcohols of the formula (IV)
R 4 OH (IV)
in which R 4 is an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds. Typical examples are caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and the like technical mixtures which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Preferred are technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol.
Die Emollients sind in den Gelen vorzugsweise in Mengen von 1 bis 20 Gew.-% und besonders bevorzugt von 5 bis 15 Gew.-% - jeweils bezogen auf das Gesamtgewicht der Gele, enthalten.The emollients are contained in the gels preferably in amounts of from 1 to 20% by weight and more preferably from 5 to 15% by weight, based in each case on the total weight of the gels.
Die Gele können optional noch Tenside, die strukturell verschieden von den Komponenten a) und b) sein müssen enthalten, und zwar nichtionisch, anionische, kationische oder vom Betaintyp, allein oder in Kombination. Bevorzugt sind anionische und/oder nichtionische Tenside.The gels may optionally contain surfactants which must be structurally different from components a) and b), nonionic, anionic, cationic or betaine type, alone or in combination. Preference is given to anionic and / or nonionic surfactants.
Typische Beispiele für anionische Tenside der erfindungsgemäßen Zubereitungen sind Seifen, Alkylbenzolsulfonate, Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersulfonate, α-Methylestersulfonate, Sulfofettsäuren, Alkylsulfate, Fettalkoholethersulfate, Glycerinethersulfate, Fettsäureethersulfate, 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.Typical examples of anionic surfactants of the preparations according to the invention are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono 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 acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially vegetable based wheat products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution.
Bevorzugt werden in den erfindungsgemäßen Gelen jedoch Alkylsulfate, Fettalkoholethersulfate, Alkansulfonate und Alkylsulfosuccinaten, besonders bevorzugt darunter die Alkyl- und/oder Alkenylsulfate, sowie die Alkylethersulfate. Unter Alkyl- und/oder Alkenylsulfaten, die auch häufig als Fettalkoholsulfate bezeichnet werden, sind die Sulfatierungsprodukte primärer Alkohole zu verstehen, die der Formel (II) folgen,
R5O-SO3X (V)
in der R5 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. 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 Roelen'schen Oxosynthese erhalten werden. Die Sulfatierungsprodukte können vorzugsweise in Form ihrer Alkalisalze und insbesondere ihrer Natriumsalze eingesetzt werden. Besonders bevorzugt sind Alkylsulfate auf Basis von C16/18-Talgfettalkoholen bzw. pflanzliche Fettalkohole vergleichbarer C-Kettenverteilung in Form ihrer Natriumsalze.However, preference is given in the gels according to the invention to alkyl sulfates, fatty alcohol ether sulfates, alkanesulfonates and alkylsulfosuccinates, particularly preferably the alkyl and / or alkenyl sulfates, and also the alkyl ether sulfates. Alkyl and / or alkenyl sulfates, which are also frequently referred to as fatty alcohol sulfates, are the sulfation products of primary alcohols which follow the formula (II),
R 5 O-SO 3 X (V)
in which R 5 is a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used according to the invention are the sulfation products of caproic alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures obtained by high-pressure hydrogenation of technical methyl ester fractions or aldehydes from the Roelen oxo synthesis. The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Particular preference is given to alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts.
Alkylethersulfate ("Ethersulfate") stellen bekannte anionische Tenside dar, die großtechnisch durch SO3- oder Chlorsulfonsäure (CSA)-Sulfatierung von Fettalkohol- oder Oxoalkoholpolyglycolethern und nachfolgende Neutralisation hergestellt werden. Im Sinne der Erfindung kommen Ethersulfate in Betracht, die der Formel (VI) folgen,
R6O-(CH2CH2O)mSO3X (VI)
in der R6 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, m für Zahlen von 0 oder 1 bis 10 und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Typische Beispiele sind die Sulfate von Anlagerungsprodukten von durchschnittlich 0 oder 1 bis 10 und insbesondere 1 bis 5 Mol Ethylenoxid an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, 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 1,5 bis 2,5 Mol Ethylenoxid an technische C12/14- bzw. C12/18- Kokosfettalkoholfraktionen in Form ihrer Natrium- und/oder Magnesiumsalze.Alkyl ether sulfates ("ether sulfates") are known anionic surfactants which are industrially produced by SO 3 or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxoalcohol polyglycol ethers and subsequent neutralization. For the purposes of the invention ether sulfates come into consideration, which follow the formula (VI),
R 6 O- (CH 2 CH 2 O) m SO 3 X (VI)
in which R 6 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, m is a number from 0 or 1 to 10 and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples are the sulfates of adducts of on average 0 or 1 to 10 and especially 1 to 5 moles of ethylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol 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. Particularly preferred is the use of ether sulfates based on adducts of on average 1.5 to 2.5 moles of ethylene oxide to technical C 12/14 - or C 12/18 - Kokosfettalkoholfraktionen in the form of their sodium and / or magnesium salts.
Typische Beispiele für nichtionische Tenside sind Fettalkoholpolyglycolether, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, gegebenenfalls partiell oxidierte Alk(en)yloligoglykoside bzw. Glucoronsäurederivate, Fettsäure-N-alkylglucamide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfettsäureester, Zuckerester, Sorbitanester, Polysorbate und Aminoxide. Sofern die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen.Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, optionally partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products). , Polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution.
Eine bevorzugte Klasse von nichtionischen Tensiden stellen die Alkyl(oligo)glycoside dar. Alkyl- und Alkenyloligoglykoside stellen bekannte nichtionische Tenside dar, die der Formel (VII) folgen,
R7O-[G]p (VII)
in der R7 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden.A preferred class of nonionic surfactants are the alkyl (oligo) glycosides. Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow formula (VII),
R 7 O- [G] p (VII)
where R 7 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.
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. Die Indexzahl p in der allgemeinen Formel (VII) 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 vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und insbesondere zwischen 1,2 und 1,4 liegt. Der Alkyl- bzw. Alkenylrest R7 kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestem oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3).The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (VII) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound, and above all If p = 1 to 6 can be assumed, the value p for one particular alkyloligoglycoside is analytically determined mathematical size, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R 7 can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis. Preference is given to alkyl oligoglucosides of the chain length C 8 -C 10 (DP = 1 to 3) which are obtained as a feedstock in the distillative separation of technical C 8 -C 18 coconut fatty alcohol and in a proportion of less than 6% by weight C 12 - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C 9/11 oxo alcohols (DP = 1 to 3).
Der Alkyl- bzw. Alkenylrest R7 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylaikohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3.The alkyl or alkenyl radical R 7 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C 12/14 coconut alcohol having a DP of 1 to 3.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden solche Gele ausgewählt, die Alky(oligo)glycoside als nichtionische Tenside enthalten, vorzugsweise in Kombination mit mindestens einem Emulgator b) ausgewählt aus einer Verbindung der allgemeinen Formel (I).In a preferred embodiment of the present invention, gels are selected which contain alky (oligo) glycosides as nonionic surfactants, preferably in combination with at least one emulsifier b) selected from a compound of general formula (I).
Weiterhin kann es vorteilhaft sein Gele auszuwählen, die als Emulgatorgemisch Partialester von einer Hydroxycarbonsäure mit einem alkoxylierten Fettalkohol zusammen mit einem alkoxylierten Fettalkohol gemäß der allgemeinen Formel (I) enthalten, ggf. aber bevorzugt in Kombination mit einen Alkyl(oligo)glycosid als nichtionisches Tensid.Furthermore, it may be advantageous to select gels containing as emulsifier partial ester of a hydroxycarboxylic acid with an alkoxylated fatty alcohol together with an alkoxylated fatty alcohol according to the general formula (I), but optionally in combination with an alkyl (oligo) glycoside as nonionic surfactant.
Typische Beispiele für kationische Tenside sind quartäre Ammoniumverbindungen und Esterquats, insbesondere quaternierte Fettsäuretrialkanolaminestersalze. Typische Beispiele für amphotere bzw. zwitterionische Tenside sind Alkylbetaine, Alkylamidobetaine, Aminopropionate, Aminoglycinate, Imidazoliniumbetaine und Sulfobetaine. Bei den genannten Tensiden handelt es sich ausschließlich um bekannte Verbindungen.Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, especially quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.
Sofern Tenside in den Gelen enthalten sind werden diese in Mengen von 1 bis 25 Gew.-% und vorzugsweise von 10 bis 20 Gew.-% - jeweils bezogen auf das Gesamtgewicht der Gele - verwendet. Es ist möglich nur eine Klasse von Tensiden zu Verwenden, wobei vorzugsweise anionische oder nichtionische Tenside ausgewählt werden, oder Mischungen von Tensiden, entweder aus einer Klasse oder aus mehreren Klassen untereinander.If surfactants are present in the gels, they are used in amounts of from 1 to 25% by weight and preferably from 10 to 20% by weight, based in each case on the total weight of the gels. It is possible to use only one class of surfactants, preferably anionic or nonionic surfactants, or mixtures of surfactants, either from one class or from several classes among themselves.
Ein weitere optionaler Bestandteil der Gele sind Kohlenwasserstoffe. Als Kohlenwasserstoffe werden organische Verbindungen bezeichnet, die nur aus Kohlenstoff und Wasserstoff bestehen. Sie umfassen sowohl cyclische als auch acyclische (= aliphatische) Verbindungen. Sie umfassen sowohl gesättigte wie einfach oder mehrfach ungesättigte Verbindungen. Die Kohlenwasserstoffe können linear oder verzweigt sein. Je nach Anzahl der Kohlenstoffatome im Kohlenwasserstoff kann man die Kohlenwasserstoffe einteilen in ungradzahlige Kohlenwasserstoffe (wie beispielsweise Nonan, Undecan, Tridecan) oder geradzahlige Kohlenwasserstoffe (wie beispielsweise Octan, Dodecan, Tetradecan). Je nach Art der Verzweigung kann man die Kohlenwasserstoffe einteilen in lineare (= unverzweigte) oder verzweigte Kohlenwasserstoffe. Gesättigte, aliphatische Kohlenwasserstoffe werden auch als Paraffine bezeichnet. Daneben können auch Benzine und Dieselöle eingesetzt werden. Die bei Raumtemperatur (21 °C) flüssigen Kohlenwasserstoffe sind generell bevorzugt.Another optional ingredient of the gels are hydrocarbons. Hydrocarbons are organic compounds that consist only of carbon and hydrogen. They include both cyclic and acyclic (= aliphatic) compounds. They include both saturated and monounsaturated or polyunsaturated compounds. The hydrocarbons can be linear or branched. Depending on the number of carbon atoms in the hydrocarbon, the hydrocarbons may be classified into odd-number hydrocarbons (such as nonane, undecane, tridecane) or even hydrocarbons (such as octane, dodecane, tetradecane). Depending on the type of branching you can divide the hydrocarbons into linear (= unbranched) or branched hydrocarbons. Saturated aliphatic hydrocarbons are also referred to as paraffins. In addition, gasolines and diesel oils can be used. The liquid at room temperature (21 ° C) hydrocarbons are generally preferred.
Paraffine sind bevorzugte Kohlenwasserstoffe im Sinne der vorliegenden Anmeldung. Die Paraffine werden vorzugsweise in Mengen von 1 bis 20 Gew.-% und vorzugsweise 1 bis 10 Gew.-% und insbesondere von 4 bis 8 Gew.-% eingesetzt. Dabei können verschiedene Qualitäten von Paraffinen zum Einsatz kommen. Es werden aber vorzugsweise bei Raumtemperatur flüssige Paraffine verwendet. Weiterhin ist die Verwendung von zwei oder mehr unterschiedlichen Kohlenwasserstoffen, vorzugsweise eines Parafinöls und von Benzin bevorzugt.Paraffins are preferred hydrocarbons in the context of the present application. The paraffins are preferably used in amounts of from 1 to 20% by weight and preferably from 1 to 10% by weight and in particular from 4 to 8% by weight. Different qualities of paraffins can be used. However, paraffins which are liquid at room temperature are preferably used. Furthermore, the use of two or more different hydrocarbons, preferably a paraffin oil and gasoline is preferred.
Die Paraffine kommen vorzugsweise in solchen Gelen zum Einsatz, die anionische Tenside als Tensidkomponente aufweisen, wobei hierbei solche Formulierungen vorteilhaft seien können, die Fettalkoholsulfate enthalten.The paraffins are preferably used in those gels which have anionic surfactants as surfactant component, in which case those formulations which contain fatty alcohol sulfates may be advantageous.
Weiterhin bevorzugt ist die Verwendung von Kohlenwasserstoffen in solchen Gel-Formulierungen, die als Emulgator Fettalkoholethoxylate der allgemeinen Formel (I) enthalten. Bevorzugte Vertreter dieser Alkoxylate folgen dann der allgemeinen Formel (I), wobei n hier im Bereich von 1 bis 10 und vorzugsweise 1 bis 6 bzw. 1 bis 5 liegt.Further preferred is the use of hydrocarbons in such gel formulations containing as emulsifier fatty alcohol ethoxylates of the general formula (I). Preferred representatives of these alkoxylates then follow the general formula (I), where n here is in the range from 1 to 10 and preferably 1 to 6 or 1 to 5.
Neben den oben beschrieben Komponenten können die Gele auch weitere Hilfs- und Zusatzstoffe enthalten. Dazu zählen Duftstoffe, Biozide, pH-Regulantien, Farbstoffe, Konservierungsstoffe, nicht-wässerige Lösungsmittel, Entschäumer, Verdicker, und/oder Desinfektionsmittel. Auch starke Säuren, insbesondere anorganische Säuren, wie HCl oder Schwefelsäure gehören zu den geeigneten Zusatzstoffen. Es kann aber auch bevorzugt sein, auf die Anwesenheit von Säuren in den gelförmigen Mitteln vollständig zu verzichten.In addition to the components described above, the gels may also contain other auxiliaries and additives. These include perfumes, biocides, pH regulants, dyes, preservatives, non-aqueous solvents, defoamers, thickeners, and / or disinfectants. Strong acids, in particular inorganic acids such as HCl or sulfuric acid are also suitable additives. However, it may also be preferable to completely dispense with the presence of acids in the gelled agents.
Diese weiteren optionalen Inhaltsstoffe sind in Summe in den Gelen in Mengen von 0,01 bis 25 Gew.-%, vorzugsweise 0,1 bis 10 Gew.-% bezogen auf das Gesamtgewicht der Gele enthalten. Von besonderer Bedeutung für Sanitärreinigungsmittel der hier vorgeschlagenen Art sind aber die Duftstoffe.These further optional ingredients are included in total in the gels in amounts of 0.01 to 25 wt .-%, preferably 0.1 to 10 wt .-% based on the total weight of the gels. Of particular importance for sanitary cleaners of the type proposed here but the fragrances.
Bei den Duftstoffen, die fest, aber vorzugsweise flüssig vorliegen, handelt es sich um teilweise komplexe Gemische aus verschiedenen chemischen Einzelverbindungen, den so genannten Riechstoffen.The fragrances, which are solid but preferably liquid, are partially complex mixtures of various individual chemical compounds, the so-called fragrances.
Die Riechstoffe können aus den verschiedensten chemischen Klassen ausgewählt werden. Man kann zwischen alkalistabilen und weniger alkalistabilen Riechstoffen unterscheiden. Alkalistabile Riechstoffe sind bevorzugt und hier können eingesetzt werden z.B. Linalool, Geraniol, Acetophenon, Lilial, Geranonitril, Dihydromyrcenol, o-tert-Butylcyclohexylacetat, Anisaldehyd, Tetrahydrolinalool, Citronellol, Cyclohexylsalicylat, Phenylethylalkohol, Benzophenon, Rosenoxid, Methylbenzoat, alpha-Hexylzimtaldehyd; zu den weniger alkalistabilen Riechstoffen gehoeren Vetiverylacetat, delta-Dodecalacton, Allylamylglycolat, Hydroxycitronellal, Benzylacetat, Amylbutyrat. Weitere geeignete Riechstoffe sind Acetophenon, Acetyleugenol, Alantwurzelöl, 1-Allyl-2,5-dimethoxy-3,4-(methylendioxy)-benzol, 1-Allyl-3-methoxy-4,5-methylen-dioxy-benzol, 1-Allyl-3,4,5-trimethoxybenzol, Allylisothiocyanat (Allylsenföl), Allyljonon, Ameisensäureethylester, Alpha-Amylzimtaldehyd, Anethol, Anisaldehyd, Apiol (Petersilienapiol), alpha-Asaron, beta-Asaron, Ascaridol, Atlanton, Baldrianöl, Benzaldehyd, Benzylaceton, Benzylalkohol ("Phenylmethanol"), Bergamotenal, Bergamotteöl, alpha-Bisabolol, Bittermandelöl blausäurefrei, cis-3-Hexen-1-ol, D-Campher, Citral, alpha-Citronellol, Costunolid, Costuswurzelöl, Diallylsulfid, 3,4-Dihydroxybenzaldehyd, 1,4-Dimethoxybenzol, Elemicin (3,4,5-Trimethoxy-1-allylbenzol), Essigsäuregeranylester, Essigsäurelinalylester, Essigsäure-2-phenylethylester, Ethylformiat, Ethylhexanoat, Ethyllaurat, Eugenol, Geranylacetat, Gurjunbalsam und Gurjunbalsamöl, Heliotropin (Piperonal), Hexahydrothymol, 1-Hexanol, Hexansäureethylester, cis-3-Hexen-1-ol, Hexylalkohol, Hydrochinon-dimethylether, Hydroxycitronellal, 4-Hydroxy-3-methoxybenzaldehyd, Jasminaldehyd, Kanadabalsam, Laurinsäureethylester, Linalool, Linalylacetat (Essigsäurelinalylester), Lorbeerblätteröl, Lyral, Menthol, Menthanon, 3,4-Methylendioxybenzaldehyd, Zimtsäuremethylester, Methyl-nonylketon (2-Undecanon), Myristicin, Nonanal (Pelargonaldehyd), alpha-Pentylzimtaldehyd, Phenol, 2-Phenylethanol, 2-Phenylethylacetat, Hydrozimtalkohol, 1-Phenyl-1-propanon, Propanal, Propiophenon (1-Phenyl-1-propanon), Rotocatechualdehyd (3,4-Dihydroxybenzaldehyd), Rhodinol, Salicylsäurebenzylester, Terpinen-4-ol, 2-Undecanon siehe Methylnonylketon, Vanillin (4-Hydroxy-3-methoxybenzaldehyd) Verbenol, Verbenon, Zimtsäuremethylester (Methylcinnamat).The fragrances can be selected from a wide variety of chemical classes. It is possible to distinguish between alkali-stable and less alkali-stable fragrances. Alkali-stable fragrances are preferred and can be used here, for example linalool, geraniol, acetophenone, lilial, geranonitrile, dihydromyrcenol, o-tert-butylcyclohexyl acetate, anisaldehyde, tetrahydrolinalool, citronellol, cyclohexyl salicylate, phenylethyl alcohol, benzophenone, rose oxide, methyl benzoate, alpha-hexyl cinnamaldehyde; the less alkali-stable fragrances include vetiveryl acetate, delta-dodecalactone, allylamyl glycolate, hydroxycitronellal, benzyl acetate, amyl butyrate. Other suitable fragrances are acetophenone, acetyleugenol, alum root oil, 1-allyl-2,5-dimethoxy-3,4- (methylenedioxy) benzene, 1-allyl-3-methoxy-4,5-methylene-dioxy-benzene, 1 Allyl-3,4,5-trimethoxybenzene, allyl isothiocyanate (allyl mustard), allyl ionone, ethyl formate, alpha-amylcinnamic aldehyde, anethole, anisaldehyde, apiol (parsley apiol), alpha-asarone, beta-asarone, ascaridol, Atlanton, valerian oil, benzaldehyde, benzylacetone, Benzyl alcohol ("phenylmethanol"), bergamotenal, bergamot oil, alpha-bisabolol, bitter almond oil cyanogen-free, cis-3-hexen-1-ol, D-camphor, citral, alpha-citronellol, costunolide, costus root oil, diallyl sulfide, 3,4-dihydroxybenzaldehyde, 1,4-dimethoxybenzene, elemicin (3,4,5-trimethoxy-1-allyl-benzene), geranyl acetate, acetic acid, 2-phenylethyl acetate, ethyl formate, ethylhexanoate, ethyl laurate, eugenol, geranyl acetate, gurjunbalsam and gum gum, heliotropin (piperonal), Hexahydrothymol, 1-hexanol, ethylhexanoate, cis 3-hexen-1-ol, hexyl alcohol, hydroquinone dimethyl ether, hydroxycitronellal, 4-hydroxy-3-methoxybenzaldehyde, jasmine aldehyde, Canada balsam, lauric acid ethyl ester, linalool, linalyl acetate (acetic acid final ester), bay leaf oil, lyral, menthol, menthanone, 3,4- Methylenedioxybenzaldehyde, cinnamic acid methyl ester, methyl nonyl ketone (2-undecanone), myristicin, nonanal (pelargonaldehyde), alpha-pentylcinnamaldehyde, phenol, 2-phenylethanol, 2-phenylethyl acetate, hydrocinnamyl alcohol, 1-phenyl-1-propanone, propanal, propiophenone (1- Phenyl-1-propanone), rotocatechualdehyde (3,4-dihydroxybenzaldehyde), rhodinol, benzyl salicylate, terpinene-4-ol, 2-undecanone see methyl nonyl ketone, vanillin (4-hydroxy-3-methoxybenzaldehyde) verbenol, verbenone, cinnamic acid methyl ester (methyl cinnamate) ,
Der Gehalt an Duftstoffen (bezogen auf das Gesamtgewicht der Gele) in den erfindungsgemäßen Gelen beträgt zwischen 0,01 und 25 Gew.-% vorzugsweise 0,01 bis 15 Gew.-%, wobei Gehalte zwischen 1,0 und 10 Gew.-% und insbesondere 1,5 bis 6 Gew.-% bevorzugt sind.The content of fragrances (based on the total weight of the gels) in the gels according to the invention is between 0.01 and 25% by weight, preferably 0.01 to 15% by weight, with contents between 1.0 and 10% by weight. and in particular 1.5 to 6 wt .-% are preferred.
Die wässerigen Gele der vorliegenden Erfindung können einen pH-Wert im Bereich von 2 bis 12, vorzugsweise 3 bis 10,5 und insbesondere von 3,5 bis 8 aufweisen, wobei der pH-Wert durch an sich übliche Basen oder Säuren eingestellt werden kann. Als Säuren werden vorzugsweise Hydroxycarbonsäuren, z.B. die Zitronensäure verwendet.The aqueous gels of the present invention may have a pH in the range of from 2 to 12, preferably from 3 to 10.5, and more preferably from 3.5 to 8, wherein the pH may be adjusted by conventional per se or acids. As acids, preferably hydroxycarboxylic acids, e.g. the citric acid used.
Als besonders bevorzugte Ausführungsform der Erfindung werden Gele beansprucht, die 10 bis 20 Gew.-% an ethoxylierten Fettalkoholen gemäß der allgemeinen Formel (I) enthält, wobei n für eine Zahl von 25 bis 35 steht, 15 bis 25 Gew.-% an weiteren Emulgatoren b) ausgewählt aus der Gruppe der Partialester von einer Hydroxycarbonsäure mit einem alkoxylierten Fettalkohol und/oder der ethoxylierten Fettsäurepolyolpartial- oder Vollester; optional 1 bis 29 Gew.-% eines Emollients gemäß der obigen Beschreibung und als Rest auf 100 Gew.-% Wasser und optional Hilfs- und Zusatzstoffe enthalten.As a particularly preferred embodiment of the invention gels are claimed which contains 10 to 20 wt .-% of ethoxylated fatty alcohols according to the general formula (I), wherein n is a number from 25 to 35, 15 to 25 wt .-% of further Emulsifiers b) selected from the group of partial esters of a hydroxycarboxylic acid with an alkoxylated fatty alcohol and / or the ethoxylated fatty acid polyol partial or full esters; optionally 1 to 29 wt .-% of an emollient according to the above description and the remainder to 100 wt .-% water and optionally auxiliaries and additives.
Ebenfalls bevorzugt sind Gele, die I) 10 bis 20 Gew.-% an ethoxylierten Fettalkoholen gemäß der allgemeinen Formel (I) enthält, wobei n für eine Zahl von 25 bis 35 steht, II) 15 bis 25 Gew.-% an weiteren Emulgatoren b) ausgewählt aus der Gruppe der Partialester von einer Hydroxycarbonsäure mit einem alkoxylierten Fettalkohol und/oder der ethoxylierten Fettsäurepolyolpartial- oder Vollester; III) optional 1 bis 29 Gew.-% eines Emollients gemäß der Beschreibung im Anspruch 12, und als Rest auf 100 Gew.-% Wasser und optional Hilfs- und Zusatzstoffe enthalten.Also preferred are gels containing I) 10 to 20 wt .-% of ethoxylated fatty alcohols according to the general formula (I), wherein n is a number from 25 to 35, II) 15 to 25 wt .-% of further emulsifiers b) selected from the group of partial esters of a hydroxycarboxylic acid with an alkoxylated fatty alcohol and / or the ethoxylated fatty acid polyol partial or full ester; III) optionally 1 to 29 wt .-% of an emollient as described in claim 12, and the remainder to 100 wt .-% water and optionally auxiliaries and additives.
Unabhängig davon sind ebenfalls bevorzugt solche Gele die 10 bis 25 Gew.-% eines anionischen Tensids, vorzugsweise ein Fettalkoholsulfat; 10 bis 20 Gew.-% eines ethoxylierten Fettalkohols gemäß der allgemeinen Formel (I) mit n von 1 bis 10; 1 bis 10 Gew.-% eines Emollients i) bis v) gemäß der obigen Beschreibung; 10 bis 20 Gew.-% eines Kohlenwasserstoffs und als Rest auf 100 Gew.-% Wasser und optional Hilfs- und Zusatzstoffe enthalten.Regardless, such gels are also preferably 10 to 25% by weight of an anionic surfactant, preferably a fatty alcohol sulfate; 10 to 20 wt .-% of an ethoxylated fatty alcohol according to the general formula (I) with n from 1 to 10; 1 to 10% by weight of an emollient i) to v) as described above; 10 to 20 wt .-% of a hydrocarbon and the balance to 100 wt .-% water and optionally auxiliaries and additives.
Die Herstellung der Gele erfolgt durch zusammenfügen der unterschiedlichen Bestandteile, wobei sowohl die an sich bekannten Heiß- als auch Kaltverfahren angewendet werden können. Heißverfahren werden insbesondere dann notwendig, wenn Bestandteile der Rezeptur bei Raumtemperatur fest sind; Diese müssen dann zunächst aufgeschmolzen und dann mit den anderen Bestandteilen vermischt werden.The preparation of the gels is carried out by combining the different components, wherein both the known hot and cold methods can be used. Hot processes become particularly necessary if ingredients of the recipe are solid at room temperature; These must then first be melted and then mixed with the other ingredients.
Die erfindungsgemäßen Gele eignen sich insbesondere als Sanitärreinigungsmittel, vorzugsweise als Sanitärreiniger die Duftstoffe frei setzen für Toiletten. Sie sind gut selbst haftend und lösen sich nicht zu schnell bei Kontakt mit insbesondere kaltem Wasser (Temperatur ≤ 20 °C und insbesondere ≤ 14 °C) auf.The gels according to the invention are particularly suitable as sanitary cleaners, preferably as sanitary cleaners set the fragrances free for toilets. They are easily self-adhesive and do not dissolve too quickly on contact with, in particular, cold water (temperature ≤ 20 ° C and especially ≤ 14 ° C).
Es wurden die folgenden Gele hergestellt und auf ihre anwendungstechnischen Eigenschaften getestet.The following gels were prepared and tested for their performance properties.
Die Herstellung erfolgte indem eine Mischung der Inhaltsstoffe ohne das Parfüm bei Raumtemperatur hergestellt wurde. Danach wurde das Gemisch erwärmt. Das Wasser wurde auf ca. 85°C und dann das Parfüm wird kalt in das heiße Gemisch eingewogen und untergerührt. Danach wurde das Wasser warm dazugegeben und auch untergerührt.The preparation was carried out by preparing a mixture of the ingredients without the perfume at room temperature. Thereafter, the mixture was heated. The water was brought to about 85 ° C and then the perfume is cold weighed into the hot mixture and stirred. Thereafter, the water was added warm and also stirred.
Alle Gele zeigten ein Brummen. Die rheologischen Eigenschaften wurden gemessen mit einem Bohlin C-VOR 120 Rheometer im Oszillationsmodus und einer 40mm Platte-Platte Meßgeometrie. Die Gele wurden mit 1 bis 100 s-1 angeregt, wobei eine Schubspannung von 50 Pa und eine 4 mm Spalthöhe gewählt wurden. Die Messung wurde bei 23 °C durchgeführt.
Im Weiteren wurden anwendungstechnische Untersuchungen vorgenommen. Es wurde hierzu ein Spültest wie folgt durchgeführt: Ca. 5g der Probe wurden auf einer Kachel verteilt und zu einem gleichmäßigen Klumpen gestrichen. Ein Wasserschlauch wurde an einem Stativ befestigt und mit einem Quetschhahn verengt, um die Stärke des Strahls zu erhöhen. Der Wasserstrahl (Temperatur des Wassers ca. 18 bis 20 °C) wurde so eingestellt dass er kurz über den Punkt aufkommt, der Wasserhahn wurde um ca. 90° geöffnet. Es wurde dann die Zeit gemessen, bis die Gelprobe abgespült war.Furthermore, application-technical investigations were carried out. For this purpose, a rinsing test was carried out as follows: Approx. 5g of the sample was spread on a tile and painted into a uniform lump. A water hose was attached to a tripod and narrowed with a pinch cock to increase the power of the jet. The water jet (temperature of the water about 18 to 20 ° C) was set so that it comes up just over the point, the faucet was opened by about 90 °. The time was then measured until the gel sample was rinsed off.
Für die Probe Nr. 5 wurde eine Zeit von 10:02 Minuten, für die Probe 8 wurde eine Zeit von 10:55 min gemessen und für die Probe 8 wurden 19:31 Minuten gemessen. Damit zeigt sich, dass die erfindungsgemäßen Gele eine ausreichend lange Zeit benötigen um mit kaltem Wasser vollständig abgespült zu werden.For Sample No. 5, a time of 10:02 minutes was measured, for Sample No. 8, a time of 10:55 minutes was measured, and for Sample No. 8, 19:31 minutes was measured. This shows that the gels according to the invention require a sufficiently long time to be completely rinsed off with cold water.
Claims (18)
R-(AO)n-H (I)
in der R für einen linearen, verzweigten, gesättigten oder ungesättigten Alkyl-oder Alkenylrest mit 12 bis 22 C-Atomen steht, AO für die Gruppen C2H4O und/oder C3H6O steht und der Index n einen Zahl von 1 bis 45, und vorzugsweise von 5 bis 35 bedeutet.Agent according to at least one of claims 1 or 2, characterized in that it contains as emulsifier b) alkoxylated fatty alcohols of the general formula (I),
R- (AO) n -H (I)
in which R is a linear, branched, saturated or unsaturated alkyl or alkenyl radical having 12 to 22 C atoms, AO is the groups C 2 H 4 O and / or C 3 H 6 O and the subscript n is a number from 1 to 45, and preferably from 5 to 35.
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WO2012041411A1 (en) * | 2010-09-30 | 2012-04-05 | Cognis Ip Management Gmbh | Air freshener gel with improved longevity |
JP2015529704A (en) * | 2012-07-16 | 2015-10-08 | レキット ベンキサー エルエルシー | Self-adhesive toilet treatment composition |
JP2015532658A (en) * | 2012-07-16 | 2015-11-12 | レキット ベンキサー エルエルシー | Toilet treatment equipment |
WO2014072677A1 (en) | 2012-11-09 | 2014-05-15 | Reckitt Benckiser Llc | Single use, foldable dispenser for an adhesive lavatory treatment composition |
EP3241887A1 (en) * | 2016-08-01 | 2017-11-08 | Clariant International Ltd | Composition comprising alcohol ethoxylate and glucamide |
WO2018024430A1 (en) * | 2016-08-01 | 2018-02-08 | Clariant International Ltd | Composition comprising alcohol ethoxylate and glucamide |
CN109563441A (en) * | 2016-08-01 | 2019-04-02 | 科莱恩国际有限公司 | Composition containing alcohol ethoxylate and glucamide |
EP3587545A1 (en) * | 2018-06-29 | 2020-01-01 | Henkel AG & Co. KGaA | Self-adhesive foaming sanitary agent |
Also Published As
Publication number | Publication date |
---|---|
RU2012129313A (en) | 2014-01-27 |
US20120252712A1 (en) | 2012-10-04 |
WO2011082751A1 (en) | 2011-07-14 |
EP2513281A1 (en) | 2012-10-24 |
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