EP2336290A1 - Préparations en forme de gel - Google Patents

Préparations en forme de gel Download PDF

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Publication number
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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EP
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Prior art keywords
alcohol
fatty alcohol
general formula
surfactants
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP09015484A
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German (de)
English (en)
Inventor
Thomas Albers
Bjoern Klotz
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Priority to EP09015484A priority Critical patent/EP2336290A1/fr
Priority to US13/515,349 priority patent/US20120252712A1/en
Priority to EP10785368A priority patent/EP2513281A1/fr
Priority to RU2012129313/04A priority patent/RU2012129313A/ru
Priority to PCT/EP2010/007403 priority patent/WO2011082751A1/fr
Publication of EP2336290A1 publication Critical patent/EP2336290A1/fr
Withdrawn legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—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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EP09015484A 2009-12-15 2009-12-15 Préparations en forme de gel Withdrawn EP2336290A1 (fr)

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EP09015484A EP2336290A1 (fr) 2009-12-15 2009-12-15 Préparations en forme de gel
US13/515,349 US20120252712A1 (en) 2009-12-15 2010-12-06 Gel-Form Preparations
EP10785368A EP2513281A1 (fr) 2009-12-15 2010-12-06 Préparations sous forme de gel
RU2012129313/04A RU2012129313A (ru) 2009-12-15 2010-12-06 Гелеобразные продукты
PCT/EP2010/007403 WO2011082751A1 (fr) 2009-12-15 2010-12-06 Préparations sous forme de gel

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WO2012041411A1 (fr) * 2010-09-30 2012-04-05 Cognis Ip Management Gmbh Gel rafraîchisseur d'air à durée de vie prolongée
WO2014072677A1 (fr) 2012-11-09 2014-05-15 Reckitt Benckiser Llc Distributeur pliable à usage unique pour une composition de traitement de toilettes adhésive
JP2015529704A (ja) * 2012-07-16 2015-10-08 レキット ベンキサー エルエルシー 自己接着性便所トリートメント組成物
EP3241887A1 (fr) * 2016-08-01 2017-11-08 Clariant International Ltd Composition comprenant un éthoxylate d'alcool et de glucamide
EP3587545A1 (fr) * 2018-06-29 2020-01-01 Henkel AG & Co. KGaA Agent sanitaire moussant autoadhésif

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EP2987850A1 (fr) * 2014-08-20 2016-02-24 Huntsman International Llc Composition de produit de nettoyage sanitaire
US10196591B2 (en) * 2015-07-10 2019-02-05 S. C. Johnson & Sons, Inc. Gel cleaning composition
US10358625B2 (en) 2015-07-17 2019-07-23 S. C. Johnson & Son, Inc. Non-corrosive cleaning composition
KR20180066109A (ko) 2015-10-07 2018-06-18 엘리멘티스 스페셜티즈, 인크. 습윤제 및 소포제
US11339353B2 (en) 2015-12-07 2022-05-24 S.C. Johnson & Son, Inc. Acidic hard surface cleaner with glycine betaine ester
EP3990603B1 (fr) * 2019-06-28 2022-12-07 Unilever Global Ip Limited Composition de détergent
WO2020260040A1 (fr) * 2019-06-28 2020-12-30 Unilever Plc Composition détergente

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Publication number Priority date Publication date Assignee Title
WO2012041411A1 (fr) * 2010-09-30 2012-04-05 Cognis Ip Management Gmbh Gel rafraîchisseur d'air à durée de vie prolongée
JP2015529704A (ja) * 2012-07-16 2015-10-08 レキット ベンキサー エルエルシー 自己接着性便所トリートメント組成物
JP2015532658A (ja) * 2012-07-16 2015-11-12 レキット ベンキサー エルエルシー 洗面所処理装置
WO2014072677A1 (fr) 2012-11-09 2014-05-15 Reckitt Benckiser Llc Distributeur pliable à usage unique pour une composition de traitement de toilettes adhésive
EP3241887A1 (fr) * 2016-08-01 2017-11-08 Clariant International Ltd Composition comprenant un éthoxylate d'alcool et de glucamide
WO2018024430A1 (fr) * 2016-08-01 2018-02-08 Clariant International Ltd Composition comprenant un éthoxylate d'alcool et un glucamide
CN109563441A (zh) * 2016-08-01 2019-04-02 科莱恩国际有限公司 含醇乙氧基化物和葡糖酰胺的组合物
EP3587545A1 (fr) * 2018-06-29 2020-01-01 Henkel AG & Co. KGaA Agent sanitaire moussant autoadhésif

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US20120252712A1 (en) 2012-10-04
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