EP2928998A1 - Détergent structuré à limite d'écoulement - Google Patents

Détergent structuré à limite d'écoulement

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Publication number
EP2928998A1
EP2928998A1 EP13795529.0A EP13795529A EP2928998A1 EP 2928998 A1 EP2928998 A1 EP 2928998A1 EP 13795529 A EP13795529 A EP 13795529A EP 2928998 A1 EP2928998 A1 EP 2928998A1
Authority
EP
European Patent Office
Prior art keywords
cleaning agent
surfactants
water
liquid detergent
sodium
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.)
Withdrawn
Application number
EP13795529.0A
Other languages
German (de)
English (en)
Inventor
Detlef Buisker
Ulrich Pegelow
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2928998A1 publication Critical patent/EP2928998A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1233—Carbonates, e.g. calcite or dolomite
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures

Definitions

  • the invention relates to a liquid detergent with yield point, containing abrasive.
  • the cleaning agent is preferably used for manual dishwashing.
  • Liquid aqueous hand dishwashing detergents are used in countless households.
  • liquid hand dishwashing detergents which also contain abrasives in order to obtain a particularly good cleaning performance even on stubborn stains.
  • structured surfactant system refers to aqueous systems which have surfactant structures that are larger than conventional spherical micelles and whose interaction thixotropes the aqueous medium
  • Lends properties These structures may be solid, mesophase, or liquid, and may be in the form of multilayer spherulites, rods, discs, or lamellae that are dispersed or emulsified discontinuously in the system or that form weak network structures.
  • L a phase in which bilayers of surfactants with the hydrophobic part of the molecule on the inside and the hydrophilic part on the outside of the bilayer (or vice versa) are located.
  • the bilayers lie side by side, for example in a parallel or concentric arrangement, sometimes separated by aqueous layers.
  • L a - phases can usually be characterized by their characteristic texture under the
  • L a phase is an L a phase at either ambient or slightly higher temperatures when mixed with water in certain specific ratios.
  • L a phases can not usually be used as structured suspending systems. Useful amounts of solids cause the systems to be no longer flowable and smaller amounts of solids tend to sediment. Also, the concentrations at which L a phases occur are often significantly higher than the usual and / or desired concentrations in liquid detergents and cleaners.
  • the main types of structured system used in practice are based on dispersed lamellar, spherulitic and attenuated lamellar phases.
  • Dispersed lamellar phases are two-phase systems in which the surfactant bilayers are arranged as parallel plates to form areas of L a phases interspersed with an aqueous phase to form an opaque gel-like system.
  • Spherolitic phases include spherical bodies, commonly referred to in the art as spherulites, in which surfactant bilayers are arranged as concentric shells.
  • the spherulites usually have a diameter in the range of 0, 1 to 15 ⁇ and are dispersed in an aqueous phase in the manner of a classic emulsion.
  • the spherulites interact to form a structured system.
  • surfactant systems are dispersed between lamellar and spherulitic.
  • the surfactant systems include both types of structures. Usually systems of a more spherulitic character are preferred because they lead to lower viscosities.
  • a third type of structured surfactant system comprises an extended L a phase. It differs from the other two structural system types in that it is essentially a single phase and from conventional L a phases in that it has a wider d-spacing.
  • Structured surfactant systems having dispersed lamellar or spherulitic phases are typically formed by the interaction of surfactants with dissolved electrolyte salts or bases.
  • Water-soluble salts have been used for some time in hard surface cleaners, for example, for viscosity adjustment or as components of buffer systems. Suspended salt particles also served as abrasives.
  • WO 2007/085410 A1 introduces a detergent composition in which salt particles can be suspended thanks to an internal structure.
  • such structured surfactant systems often have no or no sufficiently high yield strengths and / or very high amounts of electrolyte. Furthermore, there is a risk of phase separation in many systems.
  • At least one anionic surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants and mixtures thereof, at least one water-soluble inorganic salt in an amount of> 25 wt .-% and at least one water-insoluble abrasive in the form of dispersed particles.
  • Thickening agent to be able to do without has the advantage that the means simpler and
  • Embodiment the detergent free of polymeric thickener. Furthermore, the cleaning agent is stable even without the addition of another polymeric stabilizer or dispersant.
  • This detergent is particularly suitable as a hand dishwashing detergent, with the stubborn, burnt or dried dirt can be removed well.
  • Another object of the present application is accordingly the use of the
  • the cleaning agent according to the invention also has the advantage that it is washed out of a sponge more slowly than a comparable formulation without a flow limit.
  • the long shelf life in the sponge is particularly advantageous if the items to be washed are cleaned under running water, as it leads to lower losses and thus to a higher efficiency.
  • Liquid refers to the property of being flowable above the yield stress, and the term therefore also includes gels and pastes various embodiments pseudoplastic or thixotropic, preferably pseudoplastic ("shear thinning").
  • Water-soluble as used herein in connection with inorganic salts refers to the property at room temperature in water to have a solubility of> 1 g / 100g of water.
  • Water-insoluble as used herein in the context of the abrasives refers to the property of having a solubility of ⁇ 10 mg / 100 g of water at room temperature in water.
  • fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms.
  • the former are particularly preferred because of their vegetable base as based on renewable raw materials for environmental reasons, but without the teaching of the invention to them
  • the oxo alcohols or their derivatives which are obtainable, for example, by the RoELEN's oxo synthesis, can also be used correspondingly.
  • alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.
  • composition of the invention contains surfactants in a total amount of usually 7 to 40 wt .-%, preferably 10 to 35 wt .-%, in particular 12 to 25 wt .-%.
  • the surfactants contain at least one anionic surfactant selected from the group consisting of sulfonate surfactants, sulfate surfactants and mixtures thereof.
  • the content of anionic surfactant is 7 to 20 wt .-% and preferably 8 to 15 wt .-%, each based on the total cleaning agent.
  • anionic surfactant is selected from the group comprising
  • Fatty alcohol ether sulfates and mixtures thereof are particularly suitable for the preparation of stable liquid washing detergents with yield point.
  • Suitable surfactants of the sulfonate type are preferably alkylbenzenesulfonates, in particular linear C 9 .i 3 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and
  • Hydroxyalkansulfonaten and disulfonates as obtained for example from Ci 2 -8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration.
  • alkanesulfonates and the esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • the alkyl sulfonates usually have an aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated, alkyl radical having 6 to 22, preferably 9 to 20, in particular 12 to 18 and especially preferably 14 to 17 carbon atoms.
  • suitable alkyl sulfonates are the saturated alkanesulfonates, the unsaturated olefin sulfonates and the ether sulfonates which are derived formally from the alkoxylated alcohols on which the alkyl ether sulfates are based, in which terminal ether sulfonates (n-ether sulfonates) having a sulfonate function bonded to the polyether chain are present Ethersulfonate (i-ether sulfonates) with the alkyl-linked sulfonate function distinguishes.
  • alkanesulfonates in particular alkanesulfonates having a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec.
  • Na-Ci3_i7-alkanesulfonate INCI Sodium C14-17 alkyl lake sulfonates.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelklander C 2 -C 8 fatty alcohols, for example coconut fatty alcohol,
  • Tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Ci 0 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred.
  • Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • the person skilled in the art generally means, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols, ie. with aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably straight-chain, acyclic, saturated, alcohols having 6 to 22, preferably 8 to 18, in particular 10 to 16 and particularly preferably 12 to 14 carbon atoms.
  • n moles of ethylene oxide and one mole of alcohol depending on the
  • Another embodiment of the alkoxylation is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • the sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with from 1 to 6 mol of ethylene oxide very particular preference is given to the sulfuric acid monoesters of straight-chain or branched C 7 ethoxylated with from 1 to 6 mol of ethylene oxide.
  • 2 i -alcohols such as 2-methyl-branched Cg-n-alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12-18 fatty alcohols having 1 to 4 EO, in particular low-ethoxylated fatty alcohols having 1 to 4 EO, in particular 1 to 2 EO, for example 2 EO, such as Na-Ci 2 -i4-fatty alcohol + 2EO sulfate.
  • EO ethylene oxide
  • C 12-18 fatty alcohols having 1 to 4 EO in particular low-ethoxylated fatty alcohols having 1 to 4 EO, in particular 1 to 2 EO, for example 2 EO, such as Na-Ci 2 -i4-fatty alcohol + 2EO sulfate.
  • liquid detergent contains a mixture of sulfonate and sulfate surfactants.
  • fatty alcohol ether sulfates have particularly good dispersing properties.
  • the liquid cleaning agent contains a mixture of linear C 9 . 13- Alkylbenzolsulfonaten and fatty alcohol ether sulfates as anionic surfactant component.
  • the ratio of the sulfate surfactants to sulfonate surfactants is preferably in the range of 3: 1 to 1: 5, and more preferably in the range of 1: 1 to 1: 4.
  • the liquid detergent or cleaning agent contains
  • Fatty alcohol ether sulfates and C 9 .i 3 -alkylbenzenesulfonates in a mass ratio of 1: 5 to 3: 1, preferably in the range 1: 1 to 1: 4, in particular in the range 1: 4 to 1: 3.
  • the anionic surfactants are usually as alkali metal, alkaline earth metal and / or mono-, di- or Trialkanolammoniumsalz and / or but also in the form of their with the corresponding Alkali metal hydroxide, alkaline earth metal hydroxide and / or mono-, di- or trialkanolamine used in situ to be neutralized corresponding acid.
  • Preference is given here as alkali metals potassium and sodium in particular, as alkaline earth metals calcium and magnesium in particular, and as alkanolamines mono-, di- or triethanolamine. Particularly preferred are the
  • the agent according to the invention may contain, in addition to the said additional one or more further anionic surfactants, for example (secondary) alkanesulfonates, amphoteric surfactants, in particular betaine surfactants, nonionic surfactants, especially fatty alcohol polyglycol ethers and
  • further anionic surfactants for example (secondary) alkanesulfonates, amphoteric surfactants, in particular betaine surfactants, nonionic surfactants, especially fatty alcohol polyglycol ethers and
  • Alkylpolyglucoside and / or cationic surfactants, in particular for improving cleaning effect, flow behavior and / or drying behavior.
  • cationic surfactants in particular for improving cleaning effect, flow behavior and / or drying behavior.
  • the composition comprises a mixture of sulphate and sulphonate surfactants, as defined above, and additionally a nonionic surfactant.
  • Nonionic surfactants in the context of the invention are alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, endgroup-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also suitable are block polymers of ethylene oxide and propylene oxide as well as fatty acid alkanolamides and fatty acid polyglycol ethers. Important classes of nonionic surfactants according to the invention are furthermore the amine oxides and
  • the composition comprises a nonionic surfactant selected from alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides,
  • Nonionic surfactant can be in the range from 3 to 15% by weight and preferably from 4 to 10% by weight, based in each case on the total cleaning agent.
  • alkoxylated fatty alcohols are to be understood as meaning ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C 22 -alcohols having a degree of alkoxylation of up to 30, preferably ethoxylated C 18 -18 alcohols.
  • the alcohol radical may, for example, methyl branched linearly or preferably in the 2-position his or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, Ci 2 -i4 alcohols with 3 EO, 4 EO or 7 EO, C 9 _n-alcohol with 7 EO, C 13 -i 5 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-i8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C 12 -8-alcohol with 7 EO.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a Ci 6 -8 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO ..
  • the total amount of anionic and nonionic surfactant in the liquid detergent is up to 35% by weight, preferably up to 30% by weight, based on the total liquid detergent.
  • Suitable betaines which can be used in the detergent of the invention are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines. These preferably satisfy formula I,
  • Preferred betaines are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id),
  • betaines are the carbo-betaines, in particular the carbo-betaines of the formula (Ia) and (Ib), most preferably the alkylamido-betaines of the formula (Ib).
  • a preferred betaine is, for example, cocamidopropyl betaine (cocoamidopropylbetaine).
  • Sugar surfactants are known surface-active compounds, which include, for example, the sugar surfactant classes of the alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), glycerolamides, glycerol glycolipids, polyhydroxy fatty acid amide sugar surfactants (sugar amides) and alkyl polyglycosides.
  • Preferred sugar surfactants within the scope of the teaching according to the invention are the alkyl polyglycosides and the sugar amides and their derivatives, in particular their ethers and esters.
  • the ethers are the products of the reaction of one or more, preferably one, sugar hydroxy group with a compound containing one or more hydroxy groups, for example C 1.
  • the esters are the reaction products of one or more, preferably one, sugar with a carboxylic acid, in particular a C6 - 22 - fatty acid.
  • the alkyl polyglycosides (APG) preferably satisfy the general formula R'O (AO) a [G] x , in which R 'is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22, preferably 6 to 18, in particular 8 to 16 , particularly preferably 8 to 14 carbon atoms, [G] is a glycosidically linked sugar residue and x is a number from 1 to 10 and AO is an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a is the average degree of alkoxylation from 0 to 20.
  • the group (AO) a may also contain different alkyleneoxy, for example ethyleneoxy or propyleneoxy, where it is at a to the average Automatalkoxyl istsgrad, ie the sum of ethoxylation and
  • the alkyl radicals R 'of the APG are linear unsaturated radicals having the stated number of carbon atoms.
  • DP degree degree of oligomerization
  • Alkyl glycosides used with a mean degree of oligomerization x of 1, 1 to 3.0 those alkyl glycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred.
  • glycosidic sugar is preferably xylose, but especially glucose used.
  • APG are nonionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry.
  • the alkyl or alkenyl radical R ' can be derived from primary alcohols having 8 to 18, preferably 8 to 14 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol,
  • Capric alcohol and undecyl alcohol and their technical mixtures as obtained for example in the course of the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelene's oxo synthesis.
  • the alkyl or alkenyl radical R ' is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • lauryl alcohol myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • elaidyl alcohol petroselinyl alcohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof.
  • alkylpolyglycosides are, for example, C 8 -io- and C 12-14 -alkylpolyglucoside with a DP degree of 1, 4 or 1.5, in particular C 8 -alkyl-1-5-glucoside and C 12-14 -alkyl -1, 4-glucoside.
  • Suitable further anionic surfactants are in particular aliphatic sulfates such as monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.
  • aliphatic sulfates such as monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, fatty acid cyanamides, anionic sulfosuccinic acid surfactants, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarc
  • amphoteric surfactants (amphoteric surfactants, zwitterionic surfactants) which can be used according to the invention include alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the alkylamidoalkylamines are used in the context of
  • Preferred cationic surfactants are the quaternary surface-active compounds, in particular with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • Particularly preferred cationic surfactants are the quaternary ammonium compounds (QAV, INCI Quaternary Ammonium Compounds) according to the general formula (R I ) (R ") (R 1 ") (R IV ) N + X " , in which R 1 to R IV are identical or different Ci_ 2 2-alkyl radicals, C 7, 2 8-aralkyl radicals or heterocyclic radicals, where two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or
  • Imidazolinium compound, form, represent and X ⁇ are halide ions, sulfate ions, hydroxide ions or similar anions.
  • X ⁇ are halide ions, sulfate ions, hydroxide ions or similar anions.
  • at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs are prepared by reacting tertiary amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents e.g. Methyl chloride, benzyl chloride, dimethyl sulfate, dodecy
  • Suitable QAVs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, CAS No. 58390-78 6), benzoxonium chloride (benzyldodecylbis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No.
  • benzetonium chloride N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No. 121-54-0
  • dialkyldimethylammonium chlorides such as di-n -decyl-dimethyl-ammonium chloride (CAS no.
  • Preferred QUATS are the benzalkonium chlorides containing C 8 -C 8 - alkyl groups, in particular C 2 -C 4 alkyl-benzyl-dimethylammonium chloride.
  • a particularly preferred QAV is the Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5
  • Cocomonium Methosulfate Cocomonium Methosulfate; Rewoquat ® CPEM).
  • anionic surfactant-compatible and / or cationic surfactant is preferably used or omitted in a particular embodiment of the invention entirely on cationic surfactants.
  • the cleaning agent according to the invention also contains one or more water-soluble inorganic salts.
  • Inorganic salts which can be used according to the invention are preferably selected from the group consisting of colorless water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals Alkaline earth metals, aluminum and / or transition metals; Furthermore, ammonium salts can be used.
  • inorganic salts include sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, calcium chloride, magnesium chloride and mixtures thereof, since these salts are very soluble in water.
  • Particularly preferred are halides, carbonates and sulfates of the alkali metals;
  • the inorganic salt is selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium carbonate, potassium carbonate and mixtures thereof.
  • the cleaning agent according to the invention contains> 25 wt .-% of at least one water-soluble inorganic salt. It should be noted that the salt concentration in the cleaning agent according to the invention must be so high that the salt is not completely dissolved, the
  • the amount of salt is preferably in the range of> 25 to ⁇ 50 wt .-%, particularly preferably 27 to 48 wt .-%.
  • the amount of inorganic salt can be chosen such that the ratio of total amount of surfactants to inorganic salt in the range of 1: 1, 2 or less, preferably 1: (> 1, 2), for example 1: 1, 5, 1: 1, 8, 1: 2 or smaller, ie 1: (> 2).
  • the addition of the inorganic salt results in the formation of lamellar structures to an internally structured liquid cleaning agent with very good dispersing properties.
  • the liquid detergent is extremely stable and does not show any phase separation and / or precipitation of the anionic surfactants and, if present, the nonionic, amphoteric or cationic surfactants.
  • the washing or cleaning agent is macroscopically single-phase and has a yield point.
  • the yield value is preferably above 5 Pa (at room temperature, i.e., 20 ° C), more preferably 10 Pa or more, and may be, for example, 50 Pa or more, or 90 Pa or more.
  • the inorganic salt has an influence on the viscosity of the cleaning agent and with the aid of the inorganic salt, the viscosity can be adjusted so that the cleaning agent is easy to dose and a container with the cleaning agent a good
  • the agent according to the invention is structurally viscous and flowable and readily meterable when the force is above the yield point.
  • the cleaning agent is free of polymeric
  • the cleaning agent additionally contains dispersed particles of at least one abrasive.
  • the dispersed particles can along their largest spatial extent one
  • the size is chosen so that the particles on the one hand have the desired abrasive properties on the other hand but can be stably dispersed in the liquid cleaning agents.
  • the preferred size is in a range of about 5 to 100 ⁇ particle diameter.
  • Stable means that the detergents are stable at room temperature for a period of at least 4 weeks, and preferably for at least 6 weeks, without the particles creaming or sedimenting in the medium.
  • the particles can have any shape.
  • the abrasive particles may be beads containing or consisting of plastic or calcium carbonate, or powders, granules or compounds of other compounds insoluble in the detergent. Also possible are mixtures of different abrasives. Preferably, the abrasive is about
  • the liquid cleaning agents contain identical or different particles in amounts of 0.05 to 10 wt .-%, in particular 0.1 to 8 wt .-% and most preferably 0.2 to 5 wt .-%.
  • the detergents are liquid and contain water as the main solvent, i. they are aqueous cleaning agents.
  • the water content of the aqueous agent of the present invention is usually 15 to 70% by weight, preferably 20 to 60% by weight. In different
  • the water content is more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of detergent.
  • non-aqueous solvents may be added to the detergent.
  • Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range.
  • the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexyleneglycol, ethylene glycol methyl ether, ethylene glycol ethyl ether,
  • Propylene glycol propyl ether dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures thereof
  • the one or more nonaqueous solvents are usually in an amount of 0.1 to 10 wt .-%, preferably 1 to 8 wt .-% based on the
  • compositions according to the invention may contain further ingredients which further improve the performance and / or aesthetic properties of the cleaning agent.
  • additives for improving the drainage and drying behavior for adjusting the viscosity, for stabilization and other customary in manual dishwashing detergents and additives, such as UV stabilizers, perfume, pearlescing agents, dyes, corrosion inhibitors, preservatives, bittering agents, organic salts, disinfectants , Enzymes, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume, enzymes), pH adjusters and skin feel enhancing or nourishing additives.
  • Composition according to the invention one or more additives from the group of surfactants, polymers and builders (builder), usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4 wt .-%, in particular 0, 1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1, 5 wt .-%, for example 1 wt .-%.
  • the additives mentioned are dispensed with.
  • composition according to the invention may additionally contain one or more polymeric thickeners.
  • polymeric thickeners are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other customary thickening polymers.
  • Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures.
  • polysaccharide thickeners such as starches or cellulose derivatives
  • starches or cellulose derivatives may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropylmethyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • Acrylic acid polymers suitable as polymeric thickeners are, for example
  • acrylic acid copolymers are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably C-. 4- alkanols formed esters (INCI Acrylates Copolymer), which include about the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) include; (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of Ci 0 -3o-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci-4 Alkanols formed, esters (INCI acrylates / C 10-30 alkyl acrylate crosspolymer) include.
  • the content of polymeric thickener is usually not more than 8 wt .-%, preferably between 0.1 and 7 wt .-%, particularly preferably between 0.5 and 6 wt .-%, in particular between 1 and 5 wt .-% and most preferably between 1, 5 and 4% by weight, for example between 2 and 2.5% by weight.
  • the agent is free of polymeric thickeners.
  • one or more dicarboxylic acids and / or salts thereof may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, for example as available under the trade name Sokalan ® DSC is.
  • the use is advantageously carried out in amounts of 0.1 to 8 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1, 3 to 6 wt .-% and particularly preferably 2 to 4 wt .-%.
  • This component is particularly preferably used at high surfactant contents, in particular at surfactant contents above 30 wt .-%.
  • auxiliary agents and additives customary in hand dishwashing detergents and hard surface cleaners in particular UV stabilizers, perfume, pearlescing agents (INCI Opacifying Agents, for example glycol distearate, eg Cutina AGS of the company Cognis, or mixtures containing it, eg the Euperlane of the company Cognis), dyes, corrosion inhibitors, preservatives (for example the technical 2-bromo-2-nitropropane-1,3-diol (also referred to as bronopol) CAS 52-51-7) which is commercially available is), organic salts, disinfectants, enzymes, pH-adjusting agents and skin feel-improving or skin-care additives (eg dermatologically effective substances, for example, as Myacide ® BT or as Boots Bronopol BT from Boots such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein partial hydrolyzate, various vegetable protein partial
  • Plant extracts such as e.g. Aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, A.H.A. complexes, glycerol, urea, quaternized hydroxyethyl cellulose) in amounts of usually not more than 5% by weight.
  • the pH of the composition according to the invention can be determined by means of customary pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium
  • Potassium hydroxide are set, wherein - in particular with the desired hand compatibility - a range of 4 to 9, preferably 5 to 8, especially 5.5 to 7.5, is preferred.
  • the agent according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 3 wt .-%, in particular 0 , 01 to 2 wt .-%, particularly preferably 0.05 to 1 wt .-%, most preferably 0, 1 to 0.5 wt .-%, for example, 0.2 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents
  • buffer substances are the citric acid or the citrates, in particular the sodium and potassium conduction rates, for example trisodium citrate-2 H 2 O and tripotassium citrate H 2 O.
  • composition according to the invention can be used for cleaning hard surfaces, in particular for manual cleaning of dishes. Due to the contained surfactant combination, it is characterized by a good drainage and drying behavior, thanks to the abrasive effect of the abrasives it contains, it also has a very good cleaning performance even on stubborn and burnt soiling, and finally it also has a high skin friendliness.
  • the ingredients of the detergent can be mixed in stirred tanks, initially water is introduced. Then the nonaqueous solvents and surfactants are added. Subsequently, if present, the fatty acid is added and the saponification of the fatty acid portion and the neutralization of the anionic surfactants, which are used in the acid form. Then the others Ingredients, preferably in portions added.
  • the inorganic salt may be added as a solid or in the form of a concentrated solution at various times in the manufacturing process.
  • the flow limits of the detergents or cleaning agents were measured using a rotary rheometer from TA-Instruments, type AR G2. This is a so-called Schubhardskontrolliert.es rheometer.
  • the samples were loaded in the rheometer with a time-increasing shear stress s (t). For example, the shear stress in the course of 10 minutes from
  • the deformation ⁇ of the sample is measured.
  • the deformation is plotted against the shear stress in a double-logarithmic plot. If the examined sample has a yield point, clearly two areas can be distinguished in this plot.
  • Break point is possible by applying tangents to the two curve parts. Samples without yield point do not show a characteristic kink in the function ⁇ ( ⁇ ).
  • Two formulations according to the invention were prepared, the compositions of which are shown in the table below.
  • the quantities are in wt .-%.
  • the hand dishwashing detergents obtained were stable, pourable and readily dosed and had good cleaning, drainage and drying behavior.

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  • Oil, Petroleum & Natural Gas (AREA)
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  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention concerne un détergent liquide stable à limite d'écoulement et à très bonnes propriétés de dispersion. Le détergent contient au moins un tensioactif anionique, au moins un sel inorganique soluble dans l'eau et au moins un abrasif insoluble dans l'eau. L'invention concerne également l'utilisation de ce détergent.
EP13795529.0A 2012-12-04 2013-11-27 Détergent structuré à limite d'écoulement Withdrawn EP2928998A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201210222186 DE102012222186A1 (de) 2012-12-04 2012-12-04 Strukturiertes Reinigungsmittel mit Fließgrenze
PCT/EP2013/074848 WO2014086634A1 (fr) 2012-12-04 2013-11-27 Détergent structuré à limite d'écoulement

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DE102014225145A1 (de) * 2014-12-08 2016-06-09 Henkel Ag & Co. Kgaa Verfahren zur Herstellung flüssiger, Tensid-enthaltender Zusammensetzungen mit Fließgrenze
WO2016142211A1 (fr) * 2015-03-09 2016-09-15 Unilever N.V. Compositions de nettoyage concentrées stables pour surfaces dures
CN110199012B (zh) 2016-11-18 2022-05-13 联合利华知识产权控股有限公司 水性硬表面清洁组合物
DE102018214471A1 (de) 2018-08-27 2020-02-27 Henkel Ag & Co. Kgaa Verfahren zur Abfüllung einer Partikel- und Tensid-haltigen Flüssigkeit

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DK49389A (da) * 1988-02-04 1989-08-05 Colgate Palmolive Co Tixotrope, vandige maskinopvaskemidler og fremgangsmaade til fremstilling deraf
GB2434586A (en) 2006-01-24 2007-08-01 Henkel Uk Structured liquid abrasive composition
DE102009001186A1 (de) * 2009-02-26 2010-09-02 Henkel Ag & Co. Kgaa Handgeschirrspülmittel

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