EP2336290A1 - Gel-form preparations - Google Patents

Abstract

Gel-forming composition comprises: 45-90 wt.% of water; 5-35 wt.% emulsifiers; 1-25 wt.% of surfactants; and optionally further auxiliaries and additives, where the gel-forming composition has a viscous damping factor (measured at 23[deg] C) of less than 2.50 (preferably less than 1.80) Pa.s.

Description

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. 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.

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.

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 the EP 1 086 199 A1 describes gel-like agents containing fragrances, surfactants and a coupling agent, the latter 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 agent is at least 15000 mPa s.

From the WO 99/66017 are adhesive sanitary agents known which serve for cleaning and fragrancing and surfactants, water, fragrances and adhesion promoters include. After direct application to the sanitary object these Sanitänmittel rinsed only after a large number of rinsing cycles. In the EP 1 325 103 A1 Adhesive sanitary products for smooth surfaces are described. Other 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 ,

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.

It has been found that gels with certain rheological properties no longer have these disadvantages.

1. a) 45 bis 90 Gew.-% Wasser;
2. b) 5 bis 35 Gew.-% Emulgatoren und
3. c) 1 bis 25 Gew.-% Tenside sowie
4. d) optional weitere Hilfs- und Zusatzstoffe

wobei dass gelförmige Mittel einen viskosen Dämpfungsfaktor Qη (gemessen bei 23 °C) im Bereich von kleiner 2,50 Pa s und vorzugsweise kleiner 1,80 Pa s aufweist.A first subject of the present application therefore relates to a gelled agent containing, based on the total weight of the agent

1. a) 45 to 90% by weight of water;
2. b) 5 to 35 wt .-% emulsifiers and
3. c) 1 to 25 wt .-% surfactants and
4. d) optionally further auxiliaries and additives

wherein the gelled agent has a viscous damping factor Qη (measured at 23 ° C) in the range of less than 2.50 Pa s and preferably less than 1.80 Pa s.

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 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.

Such 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.

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.

gilt, wobei

• ϕ Auslenkungswinkel
• M₀ = Amplitude des Torsionsdrehmomentes
• D = Torsions-Federkonstante
• ω = Schwingungsfrequenz
• I = Trägheitsmoment
• k = Dämpfungskonstante

This also applies to the gels of the present invention. Mathematically, the system can be described as a torsion pendulum, for which the equation of motion $$I\cdot \ddot{\phi }={\mathrm{<figure-callout\; id="0"\; label="M"\; filenames="imgf0001.png"\; state="\{\{state\}\}">M</figure-callout>}}_0\cos \left(\omega \cdot t\right)-k\cdot \dot{\phi }-D\cdot \phi$$

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

As a solution of the above differential equation one obtains for the displacement A (ω) $$A\left(\omega \right)=\frac{{\mathrm{<figure-callout\; id="0"\; label="M"\; filenames="imgf0001.png"\; state="\{\{state\}\}">M</figure-callout>}}_0}{1\sqrt{{\left(\frac{D}{I}-{\omega }^2\right)}^2+\frac{{\omega }^2{k}^2}{I^2}}}$$

wobei h das Spalthöhe und r den Radius bedeuten. Q_η 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 Q_η 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 FIG. 1 the calculated curve has been compared with experimentally determined values. The measured resonance curves now depend on device parameters. The independent magnitude of the viscous damping Q _n can be calculated as follows: $$Q_n=\frac{2k\cdot H}{{\mathit{\pi r}}^4}$$

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.

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.

emulsifiers

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 alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol.

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.

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).

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.

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.

Mixtures of these ethoxylated hydroxycarboxylic acids are also suitable and preferred.

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. In particular, 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. These ethoxylation products of partial glycerides are known substances, as described, for example, in German Pat DE-C 320 24 051 (Henkel ) to be discribed. It is customary to start from partial glycerides, which are then reacted with customary alkoxylation processes to give the desired products. For this purpose, the starting materials are usually introduced in a pressure reactor, the alkaline catalyst is added, for example sodium methylate or calcined hydrotalcite, and the desired amount of ethylene oxide is pressed on. As a rule, on average 1 to 50 and preferably 5 to 20 moles of ethylene oxide are added per mole of partial glyceride. 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.

emollients

1. (i) Dialkylether, mit 8 bis 32 C-Atomen;
2. (ii) der Dialkylcarbonate mit 8 bis 32 C-Atomen;
3. (iii) Estern von Monocarbonsäuren mit einwertigen Fettalkoholen;
4. (iv) Fettalkohole mit 8 bis 32 C-Atomen,
5. (v) oder Mischungen daraus.

As emollients come within the meaning of the present technical teaching in particular:

1. (i) dialkyl ethers having 8 to 32 C atoms;
2. (ii) the dialkyl carbonates having 8 to 32 carbon atoms;
3. (iii) esters of monocarboxylic acids with monohydric fatty alcohols;
4. (iv) fatty alcohols having 8 to 32 C atoms,
5. (v) or mixtures thereof.

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)

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).

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.

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.

surfactants

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.

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.

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.

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.

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.

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. 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).

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 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).

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.

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.

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.

hydrocarbons

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.

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.

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.

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.

Auxiliaries and additives

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.

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.

fragrances

The 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. 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) ,

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. As acids, preferably hydroxycarboxylic acids, e.g. the citric acid used.

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.

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.

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.

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).

EXAMPLES

The following gels were prepared and tested for their performance properties.

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.

All the gels showed a hum. The rheological properties were measured using a Bohlin C-VOR 120 rheometer in oscillation mode and a 40mm plate-plate geometry. The gels were excited at 1 to 100 s ^-1 , with a shear stress of 50 Pa and a 4 mm gap height. The measurement was carried out at 23 ° C. number 1 ingredients Amount [wt%] C16 / 18 FA 30 EO 14 Coconut monoglyceride ethoxylated (7 EO) 20 dioctyl 5 perfume oil 5 water 56 Viscous damping factor Qη: 1.09 Pas No. 2 ingredients Amount [wt%] C16 / 18 FA 30 EO 14 Coconut monoglyceride ethoxylated (7 EO) 20 dioctyl 5 perfume oil 10 water 51 Viscous damping factor Qη: 1.29 Pas No. 3 ingredients Amount [wt%] C16 / 18 FA 30 EO 14 Hydroxycarboxylic acid partial esters of 20 alkoxylated alcohols plus APG dioctyl 5 perfume oil 5 water 56 Viscous damping factor Qη: 2.06 Pa s No. 4 ingredients Amount [wt%] C12-16 fatty alcohol sulfate sodium salt 20 Oleylcetyl alcohol ethoxylated (10 EO) 19 Octyldodecyl alcohol * 2- 2 paraffin oil 7.5 C12 / C13 alkane 10 perfume oil 5 water 36.5 Viscous damping factor Qη: 0.36 Pa s No. 5 ingredients Amount [wt%] C12-16 fatty alcohol sulfate sodium salt 20 Oleylcetyl alcohol ethoxylated (5 EO) 19 Octyldodecyl alcohol * 2- 2 17.5 41.5 Viscous damping factor Qη: 0.55 Pa s No. 6 ingredients Amount [wt%] C16 / 18 FA 30 EO 17 Hydroxycarboxylic acid partial esters of 17 alkoxylated alcohols dioctyl 5 perfume oil 5 water 56 Viscous damping factor Qη: 0.99 Pa s No. 7 ingredients Amount [wt%] C16 / 18 FA 30 EO 17 Hydroxycarboxylic acid partial esters of 17 alkoxylated alcohols plus APG dioctyl 5 C 12-14 fatty alcohol sulfate triethanolamine 5 salt perfume oil 5 water 51 Viscous damping factor Qη: 0.55 Pa s No. 8 ingredients Amount [wt%] C16 / 18 FA 30 EO 17 Hydroxycarboxylic acid partial esters of alkoxylated 17 alcohols dioctyl 5 C 12-14 fatty alcohol sulfate triethanolamine salt 5 perfume oil 10 water 46 Viscous damping factor Qη: 1.50 Pa s

Application engineering investigations

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.

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)

Gelled agent containing, based on the total weight of the agent 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 characterized in that the gel-like means have a viscous damping factor Q _η (measured at 23 ° C) in the range of less than 2.50 Pa s and preferably less than 1.80 Pa s. Means according to claim 1, characterized in that the damping factor Q _η (measured at 23 ° C) has a value in the range of 2.00 to 0.20 Pa s, and in particular in the range of 1.00 to 0.30 Pa s , 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. Composition according to one or more of claims 1 to 3, characterized in that it contains as emulsifier b) a linear, saturated fatty alcohol of the general formula (I), with 1 to 10 moles of ethylene oxide per mole of fatty alcohol, and preferably with 2 to 6 mol is ethoxylated. Agent according to one or more of claims 1 to 4, characterized in that it contains as emulsifier a partial ester of a Hydroxycarboxylic acid, preferably from the citric acid, containing an alkoxylated fatty alcohol. Agent according to at least one of claims 1 to 5, characterized in that it contains as emulsifier b) an ethoxylated Fettsäurepolyolpartial- or full ester. Agent according to at least one of claims 1 to 6, characterized in that it contains as surfactant c) anionic and / or nonionic surfactants. Composition according to at least one of claims 1 to 7, characterized in that as surfactant c) anionic surfactants, preferably selected from the group of fatty alcohol sulfates, fatty alcohol sulfonates and / or fatty alcohol ether sulfates, are included. Agent according to at least one of claims 1 to 8, characterized in that as surfactant c) nonionic surfactants selected from the group of alkyl (oligo) glycosides are included. Composition according to at least one of claims 1 to 9, characterized in that it contains partial esters of a hydroxycarboxylic acid with an alkoxylated fatty alcohol together with an alkoxylated fatty alcohol according to the general formula (I) in claim 1. Composition according to at least one of claims 1 to 10, that it contains a combination of partial esters of a hydroxycarboxylic acid with an alkoxylated fatty alcohol together with an alkoxylated fatty alcohol according to the general formula (I) in claim 1 and an alkyl (oligo) glycoside. Agent according to at least one of claims 1 to 11, characterized in that it contains as an additive at least one emollient, preferably in amounts of 1 to 20 wt .-%, selected from the group of i) dialkyl ethers having 8 to 32 carbon atoms; ii) the dialkyl carbonates having 8 to 32 carbon atoms; iii) esters of monocarboxylic acids with monohydric fatty alcohols; iv) the fatty alcohols having 8 to 32 C atoms, v) or mixtures thereof. Agent according to at least one of claims 1 to 12, characterized in that it contains at least one hydrocarbon, preferably in amounts of 1 to 20 wt .-%. Composition according to at least one of claims 1 to 13, characterized in that it contains as a hydrocarbon, a paraffin oil, gasoline or mixtures thereof. Composition according to at least one of claims 1 to 14, characterized in that it contains as surfactants c) anionic surfactants, preferably those of the fatty alcohol sulfates type, in combination with hydrocarbons. Composition according to at least one of claims 1 to 15, characterized in that it contains as additives fragrances, biocides, pH regulants, dyes, preservatives, non-aqueous solvents, defoamers, thickeners, and / or disinfectants, preferably in amounts of 0, 1 to 10 wt .-% and in particular in amounts of 1 to 5 wt .-%. Means according to at least one of claims 1 to 16, characterized in that it I) contains 10 to 20% by weight of ethoxylated fatty alcohols according to the general formula (I), where 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 Fettsäurepolyolpartial- or full esters; III) optionally 1 to 29 wt .-% of an emollient as described in claim 12, and and as balance to 100 wt .-% water and optionally auxiliaries and additives. Means according to at least one of claims 1 to 16, characterized in that it I) 10 to 25% by weight of an anionic surfactant, preferably a fatty alcohol sulphate; II) 10 to 20 wt .-% of an ethoxylated fatty alcohol according to the general formula (I) in claim 3 with n from 1 to 10; III) 1 to 10 wt .-% of an emollient as described in claim 12; IV) 10 to 20 wt .-% of a hydrocarbon and as balance to 100 wt .-% water and optionally auxiliaries and additives.

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