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EP3759205A1 - Conservation sans isothiazolinones de produits de nettoyage - Google Patents

Conservation sans isothiazolinones de produits de nettoyage

Info

Publication number
EP3759205A1
EP3759205A1 EP19704771.5A EP19704771A EP3759205A1 EP 3759205 A1 EP3759205 A1 EP 3759205A1 EP 19704771 A EP19704771 A EP 19704771A EP 3759205 A1 EP3759205 A1 EP 3759205A1
Authority
EP
European Patent Office
Prior art keywords
weight
liquid aqueous
alkyl
mixtures
aqueous cleaning
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.)
Pending
Application number
EP19704771.5A
Other languages
German (de)
English (en)
Inventor
Detlef Buisker
Marianne Schmeling
Mirko Weide
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 EP3759205A1 publication Critical patent/EP3759205A1/fr
Pending legal-status Critical Current

Links

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2034—Monohydric alcohols aromatic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers

Definitions

  • the invention relates to liquid aqueous cleaning compositions comprising: a) at least one surfactant; b) at least one salt of sorbic acid or mixtures thereof; c) at least one compound selected from benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropan-2-ol, 3-phenoxypropane-1, 2-diol, benzyloxymethanol or mixtures thereof; d) optionally additives and additives; and e) water, the sum of a) to e) being 100% by weight. Also included are a process for the preparation of the aforementioned agents and the use of a mixture of at least one salt of sorbic acid or
  • Liquid aqueous detergents in particular hand dishwashing detergents, are generally preserved with isothiazolinone or derivatives thereof, in particular methylisothiazolinone (MIT), benzisothiazolinone (BIT) or octylisothazolinone (OIT), as a preservative.
  • MIT methylisothiazolinone
  • BIT benzisothiazolinone
  • OIT octylisothazolinone
  • Composition to provide and which also more compatible or less
  • the inventors of the present invention have found that this is achieved by using a mixture of at least one salt of sorbic acid or mixtures thereof; and at least one compound selected from benzyl alcohol, 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropan-2-ol, 3-phenoxypropane-1, 2-diol, benzyloxymethanol or mixtures thereof.
  • This will be watery
  • a first subject of this application are therefore liquid aqueous cleaning agents, hereinafter also referred to as agents according to the invention, comprising or consisting of:
  • benzyl alcohol 2-phenylethyl alcohol, 2-phenoxyethanol, 3-phenoxypropanol, 1-phenoxypropan-2-ol, 3-phenoxypropane-1,2-diol, benzyloxymethanol or mixtures thereof;
  • composition according to the invention can be used for cleaning hard surfaces and for manual dishwashing.
  • alkaline earth metals are referred to below as counter ions for monovalent anions, this means that the alkaline earth metal is only in half - to charge balance
  • % by weight refers to the entire liquid aqueous cleaning agent. These percentages refer to active contents.
  • the water content of the aqueous composition according to the invention is usually 15 to 98% by weight, preferably 20 to 95% by weight, in particular 30 to 90% by weight.
  • the agent of the invention is free of isothiazolinone and its derivatives, in particular methylisothiazolinone (MIT), benzisothiazolinone (BIT) or octylisothazolinone (OIT).
  • MIT methylisothiazolinone
  • BIT benzisothiazolinone
  • OIT octylisothazolinone
  • the composition according to the invention contains surfactants in a total amount of usually 3 to 50% by weight, preferably 5 to 35% by weight, in particular 7 to 15% by weight.
  • the liquid aqueous cleaning agent of the present invention comprises anionic and / or amphoteric surfactants.
  • the liquid aqueous cleaning agent of the present invention comprises at least one amphoteric surfactant selected from betaines, sulfobetaines or a mixture thereof.
  • the liquid aqueous cleaning agent of the present invention comprises at least one anionic surfactant selected from alkyl ether sulfates, secondary alkanesulfonates, fatty alcohol sulfates, monoglyceride sulfates, ester sulfonates, lignosulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic surfactant selected from alkyl ether sulfates, secondary alkanesulfonates, fatty alcohol sulfates, monoglyceride sulfates, ester sulfonates, lignosulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic surfactant selected from alkyl ether sulfates, secondary alkanesulfonates, fatty alcohol sulfates, monoglyceride sulfates, ester sulfonates, lignosulfonates, alkyl
  • Sulfosuccinic acid surfactants fatty acid isethionates, acylaminoalkanesulfonates,
  • Fatty acid sarcosinates ether carboxylic acids, alkyl (ether) phosphates and gemini surfactants, or a mixture thereof, preferably an alkyl ether sulfate, more preferably sodium lauryl ether sulfate.
  • it comprises at least one amphoteric surfactant and at least one anionic surfactant, more preferably selected from the specific surfactants mentioned above.
  • the agent according to the invention can be any suitable agent according to the invention.
  • the agent according to the invention can be any suitable agent according to the invention.
  • alkyl ether sulfate, secondary alkyl sulfonate and betaine contain, in other preferred forms can be additionally included alkyl polyglycosides.
  • the anionic surfactants are usually in situ as the alkali metal, alkaline earth metal and / or mono-, di- or trialkanolammonium salt and / or else in the form of theirs with the corresponding alkali metal hydroxide, alkaline earth metal hydroxide and / or mono-, di- or trialkanolamine to be neutralized corresponding acid used.
  • Preferred alkali metals here are potassium and in particular sodium, alkaline earth metals calcium and in particular magnesium, and alkanolamines mono-, di- or triethanolamine. Particularly preferred are the
  • Suitable anionic surfactants are especially the alkyl ether sulfates and secondary alkanesulfonates.
  • aliphatic sulfates such as fatty alcohol sulfates, monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, alkylbenzenesulfonates, fatty acid cyanamides, anionic sulfosuccinic acid, fatty acid isethionates, acylaminoalkanesulfonates
  • anionic surfactants are anionic gemini surfactants having a diphenyloxide basic structure, 2 sulfonate groups and one alkyl radical on one or both benzene rings according to the formula O 3 S (C 6 H 3 R) O (C 6 H 3 R ') SO 3, in which R is an alkyl radical with, for example, 6, 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax® Dry Hydrotropes with Ci6-alkyl radical (s); INCI: Natriumhexyldiphenylethersulfonat,
  • Disodium decylphenyl ether disulfonate disodium lauryl phenyl ether disulfonate
  • Disodium cetylphenyl ether disulfonate and fluorinated anionic surfactants, especially perfluorinated alkyl sulfonates such as ammonium C9 / io perfluoroalkyl sulfonate (Fluorad® FC 120) and
  • composition according to the invention may contain anionic surfactants in amounts of 1 to 30% by weight, preferably 5 to 15% by weight, in particular 7 to 10% by weight.
  • Alkyl ether sulfates (fatty alcohol ether sulfates, INCI: alkyl ether sulfates) are products of
  • alkoxylated alcohols 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.
  • Alkoxylation is the use of mixtures of alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • Very particularly preferred for the purposes of the present invention are low-ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 2 EO, such as Na-Ci 2 -i 4 -fatty alcohol + 2EO sulfate.
  • EO ethylene oxide units
  • a particularly preferred compound is sodium dodecylpoly (oxyethylene) sulfate with 3 EO.
  • the composition according to the invention comprises one or more alkyl ether sulfates in an amount of 1 to 30% by weight, preferably 5 to 15% by weight, in particular 7 to 10% by weight.
  • alkyl sulfonates usually have an aliphatic straight-chain or mono- or poly-branched, acyclic or cyclic, saturated or mono- or polyunsaturated, preferably branched, acyclic, saturated, alkyl radical having 6 to 22, preferably 9 to 20, in particular 11 to 18 and particularly preferred 14 to 17
  • 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 bound to the polyether chain and internal radicals Ether sulfonates (i-ether sulfonates) with sulfonate function linked to the alkyl radical
  • alkanesulfonates in particular alkanesulfonates having a branched, preferably secondary, alkyl radical, for example the secondary alkanesulfonate sec. Na-Cz-alkanesulfonate.
  • the agent according to the invention contains one or more sec. Alkyl sulfonates in an amount of 1 to 30% by weight, preferably 5 to 15% by weight, in particular 7 to 10% by weight.
  • alkylbenzenesulfonates ABS for short, especially linear alkylbenzenesulfonates (LAS). These usually have the benzene ring in addition to a sulfonic acid or sulfonate also an aliphatic straight-chain or mono- or poly-branched, acyclic, saturated or mono- or polyunsaturated alkyl side chain with 6 to 22, preferably 8 to 20, especially 10 to 16 and particularly preferably 12 until 14
  • Alkylbenzenesulfonates are used in the composition according to the invention preferably in amounts of 1 to 30% by weight, preferably 5 to 15% by weight, in particular 7 to 10% by weight.
  • Suitable alkyl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 20 -oxo alcohols and those monoesters secondary Alcohols of these chain lengths are preferred.
  • alkyl sulfates of said chain length which are synthetic, petrochemical Basis produced straight-chain alkyl radical containing an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • Particularly preferred are the Cio -i6-alkyl sulfates, in particular the Ci 2-14 alkyl sulfates.
  • composition according to the invention may contain one or more alkyl sulfates in amounts of preferably 0.1 to 10% by weight, more preferably 0.5 to 6% by weight, in particular 1 to 3% by weight.
  • Particularly preferred further anionic surfactants are the anionic ones
  • Succinic acid surfactants Sulfosuccinates, sulfosuccinamates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates.
  • the sulfosuccinates are the salts of the mono- and diesters of sulfosuccinic acid H00CCH (SO 3 H) CH 2 C00H, while the sulfosuccinamates are the salts of
  • the salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or potassium salts
  • Ammonium salts more preferably sodium or ammonium salts, most preferably sodium salts.
  • one or both carboxyl groups of the sulfosuccinic acid is preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols having 4 to 22, preferably 6 to 20, in particular 8 to 18 , more preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified.
  • esters of unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols in particular unbranched, saturated fatty alcohols and / or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols having a degree of alkoxylation of 1 to 20, preferably 1 to 15, in particular 1 to 10, more preferably 1 to 6, most preferably 1 to 4.
  • the monoesters are preferred in the context of the present invention over the diesters.
  • a particularly preferred sulfosuccinate is Sulfobernsteinklarylpolyglykolester di-sodium salt (lauryl EO sulfosuccinate, di-Na salt), for example, as Tego® sulfosuccinate (Evonik Tego Chemie GmbH) with a
  • Sulphosuccinate content of 30% by weight is commercially available.
  • one or both carboxyl groups of sulfosuccinic acid forms preferably with a primary or secondary amine which has one or two identical or different, unbranched or branched, saturated or unsaturated, Acyclic or cyclic, optionally alkoxylated alkyl radicals having 4 to 22, preferably 6 to 20, in particular 8 to 18, particularly preferably 10 to 16, most preferably 12 to 14
  • Carbon atoms a carboxylic acid amide.
  • Particular preference is given to unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals.
  • Also suitable are, for example, those disclosed in WO 2008/046778 A1
  • Sulfosuccinamates and sulfosuccinamides which are explicitly referred to.
  • Yet another suitable sulfosuccinamate is disodium C 1-8 alkoxy propylene sulfosuccinamate.
  • Preferred anionic sulfosuccinic acid surfactants are imidosuccinate, monosulfosuccinic acid di-isobutyl ester (Monawet® MB 45), mono-sulfosuccinic acid dioctyl ester (Monawet® MO-84 R2W, Rewopol® SB DO 75), mono-sodium sulfosuccinic acid di-tridecyl (Monawet® MT 70) Fettalkoholpolyglykolsulfosuccinat-Na-NFU salt (S- sulfosuccinate 2), di-Na-sulfosuccinic acid mono-Ci 2 / 3EO-i4 ester (Texapon SB-3),
  • Diisooctyl sodium sulfosuccinate (Texin® DOS 75) and di-Na-sulfosuccinic acid mono-C 12/18 esters (Texin® 128-P), in particular the monosodium sulfosuccinic acid di-octyl ester.
  • the agent according to the invention contains as anionic
  • Sulfosuccinic acid surfactants one or more sulfosuccinates, sulfosuccinamates and / or sulfosuccinamides, preferably sulfosuccinates and / or sulfosuccinamates, in particular sulfosuccinates, in an amount of usually 0.001 to 5% by weight, preferably 0.01 to 4% by weight, in particular 0.1 to 3 % By weight, particularly preferably 0.2 to 2% by weight, very preferably 0.5 to 1.5% by weight, for example 1% by weight.
  • anionic surfactants are, in particular, anionic gemini surfactants having a diphenyloxide basic structure, 2 sulfonate groups and an alkyl radical on one or both benzene rings of the formula O 3 S (C 6 H 3 R) O (C 6 H 3 R ') SO 3 ' , in which R is an alkyl radical having, for example, 6 , 10, 12 or 16 carbon atoms and R 'is R or H (Dowfax® Dry Hydrotropes with Ci6-alkyl radical (s), INCI: Natriumhexyldiphenyletheresulfonat,
  • Disodium decylphenyl ether bisulfonates disodium lauryl phenyl ether disulfonate
  • Disodium cetylphenyl ether disulfonates and the fluorinated anionic surfactants ammonium C9 / perfluoroalkylsulfonate (Fluorad® FC 120), perfluorooctanesulfonic acid potassium salt (Fluorad® FC 95) and the sulfosuccinic acid surfactants imidosuccinate, mono-Na-sulfosuccinic acid di-isobutyl ester (Monawet® MB 45), monosodium sulfosuccinic acid di-octyl ester (Monawet® MO 84 R2W, Rewopol® SB DO 75), monosodium sulfosuccinic acid di-tridecyl ester (Monawet® MT 70), fatty alcohol polyglycol sulfosuccinate Na-NFU salt ( Sulfosuccinate S-2), di-Na-sulfosucc
  • Betaine Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazoliumbetaines, the sulfobetaines (INCI: sultaines) and the phosphobetaines and preferably satisfy formula I, R 1 - [CO-X- (CH 2) n] x N + (R 2 ) (R 3 ) - (CH 2) m - [CH (OH) - CH 2] y - Y ⁇ (I) in which
  • R 1 is a saturated or unsaturated C6 22 alkyl, preferably Cs -is-alkyl radical, particularly a saturated Cio -i6 alkyl group, for example a saturated Ci2-14 alkyl radical,
  • X is NH, NR 4 with a Ci- 4 alkyl group R 4, O or S,
  • n is a number from 1 to 10, preferably 2 to 5, in particular 3,
  • x is 0 or 1, preferably 1,
  • R 2 , R 3 are independently a C- alkyl radical, optionally hydroxy-substituted such.
  • n is a number from 1 to 4, in particular 1, 2 or 3,
  • y is 0 or 1
  • R 5 is a hydrogen atom H or a C1-4 alkyl radical.
  • 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),
  • R 1 is -N + (CH 3 ) 2 -CH 2 COO- (la)
  • 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).
  • betaines and sulfobetaines are e.g. in WO 2008/046778 A1, to which reference is explicitly made.
  • a preferred betaine is, for example
  • Cocoamidopropyl betaine or betaine which is commercially available under the trade name Tego® Natural Betaine from Evonik.
  • the agent according to the invention may contain one or more betaines in an amount of preferably 0.1 to 15% by weight, more preferably 1 to 10% by weight, in particular 2 to 5% by weight.
  • the composition according to the invention may contain a surfactant combination of a) alkyl ether sulfate, b) secondary alkanesulfonate and c) betaine, wherein said surfactants are preferably present in a ratio a) b) c) of 5: 2: 1 to 3: 1: 1.
  • amphoteric surfactants are amphoteric surfactants.
  • 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 betaines are preferred within the scope of the teaching according to the invention.
  • alkylamidoalkylamines are amphoteric surfactants of the formula (III), R 9 -CO-NR 10 - (CH 2 ) iN (R 11 ) - (CH 2 CH 2 O) j (CH 2 ) k - [CH (OH)] i -CH2-Z-OM (III), in the
  • R 9 is a saturated or unsaturated C 6-22 -alkyl radical, preferably C 1 -is-alkyl radical, in particular a saturated C 10 -alkyl radical, for example a saturated C 2-14 -alkyl radical,
  • R 10 is a hydrogen atom H or a Ci- 4 alkyl group, preferably H,
  • i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
  • R 11 is a hydrogen atom H or CH 2 COOM
  • j is a number from 1 to 4, preferably 1 or 2, in particular 1,
  • k is a number from 0 to 4, preferably 0 or 1
  • Z is CO, SO2, OPO (OR 12) or P (0) (0R 12), wherein R 12 is Ci- 4 alkyl or M (defined as follows), and
  • M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine.
  • alkylamidoalkylamines are e.g. those disclosed in WO 2008/046778 A1, to which reference is explicitly made.
  • amphoteric surfactants are in particular
  • Alkyl-substituted amino acids which are preferred according to the invention are monoalkyl-substituted
  • R 13 is -NH-CH (R 14 ) - (CH 2 ) U-COOM '(IV) in which
  • R 13 is a saturated or unsaturated C 6-22 -alkyl radical, preferably C 1 -is-alkyl radical, in particular a saturated C 10 -alkyl radical, for example a saturated C 2-14 -alkyl radical, R 14
  • u is a number from 0 to 4, preferably 0 or 1, in particular 1, and
  • M ' is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine,
  • R 15 is a saturated or unsaturated C 6-22 -alkyl radical, preferably C 1 -is-alkyl radical, in particular a saturated C 10 -alkyl radical, for example a saturated C 2-14 -alkyl radical,
  • v is a number from 1 to 5, preferably 2 or 3, in particular 2, and
  • M represents a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M" in the two carboxy groups may have the same or different meanings, e.g. Hydrogen and sodium or twice sodium may be
  • R 16 is a saturated or unsaturated C 6-22 -alkyl radical, preferably C 1 -is-alkyl radical, in particular a saturated C 10 -alkyl radical, for example a saturated C 2-14 -alkyl radical, R 17
  • Hydrogen atom or a Ci- 4 alkyl group optionally hydroxy or amino substituted, for example a methyl, ethyl, hydroxyethyl or Aminpropylrest,
  • R 18 is the residue of one of the 20 natural ⁇ -amino acids, H 2 NCH (R 18 ) COOH, and M '''is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, eg protonated mono-, di- or triethanolamine.
  • alkyl-substituted amino acids are the aminopropionates according to formula (IVa),
  • exemplary suitable alkyl-substituted amino acids are disclosed in WO 2008/046778 A1, to which reference is explicitly made.
  • Acylated amino acids are amino acids, in particular the 20 natural a-amino acids which carry on the amino nitrogen the acyl radical R 19 CO of a saturated or unsaturated fatty acid R 19 COOH, where R 19 is a saturated or unsaturated C 6-22 -alkyl radical, preferably Cs -is-alkyl radical , in particular a saturated Cio-i6-alkyl radical, for example a saturated Ci 2-14 alkyl radical.
  • the acylated amino acids may also be used as alkali metal salt, alkaline earth metal salt or
  • Alkanolammonium salt e.g. Mono-, di- or Triethanolammoniumsalz be used.
  • acylated amino acids are those listed under INCI under Acids: acyl derivatives, e.g. Sodium cocoylglutamate, lauroylglutamic acid, capryloylglycine or
  • a combination of two or more different amphoteric surfactants in particular a binary Amphotensidkombination is used.
  • the amphoteric surfactant combination preferably contains at least one betaine, in particular at least one alkylamidobetaine, more preferably cocoamidopropylbetaine. Furthermore, the amphoteric surfactant combination preferably contains at least one amphoteric surfactant from the group comprising sodium carboxyethyl cocosphoethyl imidazoline (Phosphoteric® TC6), cocoamidopropyl betaine (INCI: caprylic / capramidopropyl betaine, Tego® Betaine 810), N-2-hydroxyethyl-N-carboxymethyl fatty acid amido ethylamine-Na (Rewoteric® AMV) and N-capryl / caprinamidoethyl-N-ethyl ether-propionate-Na (Rewoteric® AMVSF) and the betaine 3- (3-cocoamido-propyl) -dimethylammonium-2-hydroxypropanesulfon
  • the agent according to the invention contains one or more amphoteric surfactants in an amount of more than 0.1% by weight and less than 8% by weight, preferably less than 5% by weight, less than 3% by weight.
  • composition according to the invention may additionally contain one or more nonionic surfactants, usually in an amount of from 0.1 to 15% by weight, preferably from 0.25 to 10% by weight, in particular from 0.5 to 6% by weight.
  • nonionic surfactants in the context of the invention are alkoxylates such as polyglycol ethers,
  • Fatty alcohol polyglycol ethers alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters.
  • block polymers of ethylene oxide and propylene oxide and fatty acid alkanolamides are also suitable.
  • nonionic surfactants are furthermore the amine oxides and the sugar surfactants, in particular the alkyl polyglucosides, as well as the biosurfactants (glycolipids).
  • fatty alcohol polyglycol ethers are to be understood as meaning, with ethylene (EO) and / or propylene oxide (PO), alkoxylated, unbranched or branched, saturated or unsaturated C 10-22 alcohols having a degree of alkoxylation of up to 30, preferably ethoxylated C 16 -C 16 fatty alcohols having a Degree of ethoxylation of less than 30, preferably with a degree of ethoxylation of 1 to 20, in particular from 1 to 12, particularly preferably from 1 to 8, most preferably from 2 to 5, for example Ci 2 -i 4 -Fettalkoholethoxylate with 2, 3 or 4 EO or a mixture of the C12 fatty alcohol with 14 EO 3 and 4 in a weight ratio of 1 to 1 or
  • amine oxides suitable according to the invention include alkylamine oxides, in particular
  • Alkyldimethylamine oxides alkylamidoamine oxides and alkoxyalkylamine oxides.
  • Preferred amine oxides satisfy formula II,
  • R 6 is a saturated or unsaturated C6-22-alkyl radical, preferably Cs -is-alkyl radical, in particular a saturated Cio-i6-alkyl radical, for example a saturated C 2-14 -alkyl radical which is substituted in the
  • B. is a hydroxyethyl radical, in particular a methyl radical.
  • Suitable amine oxides are disclosed in WO 2008/046778 A1, to which reference is explicitly made.
  • a preferred amine oxide is, for example, cocamidopropylamine oxides (cocoamidopropylamine oxide)
  • Sugar surfactants are known surface-active compounds, to which, for example, the sugar surfactant classes of the alkyl glucose esters, aldobionamides, gluconamides (sugar acid amides), Glycerin amides, 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 hydroxyl groups, for example C-22 alcohols or glycols such as ethylene and / or propylene glycol, where the sugar hydroxy group also polyethylene glycol and /or
  • Polypropylene glycol can carry.
  • the esters are the reaction products of one or more, preferably one, sugar hydroxy group with a carboxylic acid, in particular a C6-22 fatty acid.
  • Particularly preferred sugar amides satisfy the formula R'C (O) N (R ") [Z], in which R 'is a linear or branched, saturated or unsaturated acyl radical, preferably a linear unsaturated acyl radical, having 5 to 21, preferably 5 to 17, in particular 7 to 15, particularly preferably 7 to 13 carbon atoms, R "is a linear or branched, saturated or unsaturated alkyl radical, preferably a linear unsaturated alkyl radical, having 6 to 22, preferably 6 to 18, in particular 8 to 16, particularly preferred 8 to 14 carbon atoms, a Ci-5-alkyl radical, in particular a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or n-pentyl radical, or hydrogen and Z is a sugar residue, ie one
  • sugar amides are the amides of glucose, the glucamides, for example lauroyl-methyl-glucamide.
  • alkylpolyglycosides are particularly preferred sugar surfactants within the scope of the teaching according to the invention and 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] for a glycosidically linked sugar residue and x for a number from 1 to 10 and AO for an alkyleneoxy group, for example an ethyleneoxy or propyleneoxy group, and a represent the average degree of alkoxylation of 0 to 20.
  • R'O (AO) a [G] x in which R 'is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 , preferably 6 to 18, in particular 8 to 16, particularly preferably 8 to 14 carbon atoms, [G] for a glycosidically linked sugar residue and x for a number from 1 to 10
  • the group (AO) a may also contain different alkyleneoxy units, for example ethyleneoxy or propyleneoxy units, in which case a is the average total degree of alkoxylation, ie the sum of degree of ethoxylation and degree of propoxylation.
  • alkyl radicals R 'of the APG are linear unsaturated radicals having the specified number of carbon atoms.
  • APG are nonionic surfactants and are known substances that can be obtained by the relevant methods of preparative organic chemistry.
  • alkyl glycosides are preferred whose Oligomens mecanicsgrad less than 1, 7 and in particular between 1, 2 and 1, 6 is.
  • the glycosidic sugar used is preferably xylose, but especially glucose.
  • the alkyl or alkenyl radical R ' can be derived from primary alcohols having 8 to 18, preferably 8 to 14 carbon atoms. Typical examples are caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, such as those obtained during the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from ROELEN's oxosynthesis.
  • the alkyl or alkenyl radical R ' is derived from lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol or oleyl alcohol.
  • elaidyl alcohol, Petroselylalkohol, arachidyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and their technical mixtures may be mentioned.
  • alkyl polyglycosides are, for example Cs -io- and a C 12-14 alkyl polyglucoside with an average degree of 1, 4 or 1, 5, in particular C8-io-alkyl-1, 5-glucoside and C 2-14 alkyl 1, 4-glucoside.
  • a likewise particularly suitable class of nonionic surfactants are so-called biosurfactants, which are glycolipids of microbial origin, for example sophorolipids, rhamnolipids, glucoselipids, cellobioselipids or trehaloselipids.
  • Glycolipids in the narrower sense are compounds in which one or more monosaccharide units are glycosidically linked to a lipid moiety. They are among the biosurfactants, by which one understands surface-active substances of microbial origin, based on vegetable oil or
  • Sugar substrates can be produced.
  • sophorolipids are produced by fermentation using yeasts such as Candida bombicola (also known as Torulopsis bombicola), Yarrowia lipolytica, Candida apicola (Torulopsis apicola) and Candida bogoriensis, growing them on sugars, hydrocarbons, vegetable oils or mixtures thereof. That under the
  • Sopholiance S available from the company Soliance sophorolipid is obtained for example by fermentation of Candida bombicola on rapeseed oil methyl ester and glucose.
  • Receives rhamnolipids on the other hand, bacteria of the genus Pseudomonas, in particular Pseudomonas aeruginosa, are preferred for growth on hydrophobic substrates such as n-alkanes or vegetable oils.
  • Glycolipids such as glucoselipids, cellobioselipids or trehaloselipids
  • Glycolipids are produced by other microorganisms on different substrates.
  • glycolipid biosurfactants are selected from the group comprising sophorolipids, rhamnolipids, glucoselipids, cellobioselipids, trehaloselipids and mixtures thereof, with particular preference being given to sophorolipids and / or
  • nonionic surfactants are, in particular, ci-dimethylamine oxide (Ammonyx® DO), Cio-14-fatty alcohol + 1, 2PO + 6,4EO (Dehydol® 980), C 12/14 fatty alcohol + 6EO (Dehydol® LS6), C 8 fatty alcohol +1, 2PO + 9EO (Dehydol® 010), Ci6 / 20-Guerbet alcohol + 8EO, n-butyl-capped (Dehypon® G2084), mixture of several n-butyl-closed nonionic surfactants and Cs / io-APG (Dehypon® Ke 2555), C8 / io-fatty alcohol + 1 PO + 22EO- (2-hydroxydecyl) -ether (Dehypon® Ke 3447), Ci2 / i4-fatty alcohol + 5EO + 4PO (Dehypon® LS 54 G), Ci2 / i4-fatty alcohol + 5 EO + 3PO,
  • the cleaning agent according to the invention may further comprise one or more water-soluble salts which serve, for example, for adjusting the viscosity. It may be inorganic and / or organic salts, in a preferred embodiment, the agent contains at least one inorganic salt.
  • 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, also ammonium salts can be used.
  • Particularly preferred are halides and sulfates of the alkali metals, preferably the inorganic salt is therefore selected from the group comprising
  • the organic salts which can be used according to the invention are in particular colorless water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and / or Transition metal salts of carboxylic acids.
  • the salts are selected from the group comprising formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.
  • a particularly preferred salt is the as
  • the agent according to the invention may advantageously additionally comprise one or more water-soluble organic solvents, usually in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight, in particular 2 to 15% by weight, more preferably 3 to 12% by weight, most preferably 4 to 8% by weight.
  • the agent according to the invention is free of organic solvents.
  • the solvent is used in the context of the teaching of the invention as needed in particular as a hydrotrope, viscosity regulator and / or cold stabilizer. It works
  • solubilizing especially for surfactants and electrolyte and perfume and dye and thus contributes to their incorporation, prevents the formation of liquid-crystalline phases and has a share in the formation of clear products.
  • the viscosity of the agent according to the invention decreases with increasing amount of solvent. However, too much solvent can be too strong
  • Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C-i-20-hydrocarbons, preferably C 2-15 -hydrocarbons, having at least one hydroxy group and optionally one or more ether functions C-O-C, i. disrupt the carbon atom chain
  • Preferred solvents are the - optionally unilaterally etherified with a C1-6 alkanol - C2-6-alkylene glycols and poly-C 2 -3-alkylene glycol ethers having on average 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule as well as the 6-alcohols, preferably ethanol, n-propanol or iso-propanol, in particular ethanol.
  • Exemplary solvents are disclosed in WO 2008/046778 A1, to which reference is explicitly made.
  • Particularly preferred solvents are the unilaterally etherified with a Ci e-alkanol poly-C2-3-alkylene glycol ethers having an average of 1 to 9, preferably 2 to 3, ethylene or
  • Propylene glycol groups for example PPG-2 methyl ether (dipropylene glycol monomethyl ether).
  • the solvent is selected from the group comprising methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol and mixtures thereof
  • Extremely preferred solvents are the C 2 -3-alcohols ethanol, n-propanol and / or iso-propanol, in particular ethanol.
  • solubilizer in particular for perfume and dyes, for example, alkanolamines and alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical can be used in addition to the solvents described above.
  • compositions according to the invention may contain further additives.
  • additives include, for example, other surfactants, microcapsules, 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, organic Salts, disinfectants, enzymes and pH adjusters.
  • composition of the invention may additionally comprise one or more cationic surfactants
  • cationic surfactants INCI: quaternary ammonium compounds
  • Preferred cationic surfactants are the quaternary surface-active compounds, in particular having an ammonium, sulfonium, phosphonium, iodonium or arsonium group.
  • Particularly preferred cationic surfactants are the quaternary ones
  • Ammonium compounds according to the general formula (R ') (R ") (R"') (R 'V) N + X in which R' to R 'v identical or different C1-22 - alkyl radicals, C7 represent 28 -aralkyl radicals, or heterocyclic radicals, or in the case of an aromatic compound such as pyridine-even three groups together with the nitrogen atom forming the heterocycle, for example a pyridinium or imidazolinium form, and X 'is halide ions, sulfate ions, Hydroxide ions or similar anions are.
  • At least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions.
  • Amines which have three long alkyl radicals or hydroxy have substituted alkyl radicals, are less reactive and are preferably quaternized with dimethyl
  • QAVs examples include benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 1-2 -alkylammonium chloride, CAS No. 58390-78-6).
  • Benzoxonium chloride (benzyldodecylbis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No 57-09-0), benzetonium chloride (N, N-dimethyl-N [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No 121-54-0),
  • Dialkyldimethylammonium chloride such as di-n-decyldimethylammonium chloride (CAS No 7173-51 -5-5), didecyldimethylammonium bromide (CAS No 2390-68-3), dioctyldimethylammonium chloride, 1-cetylpyridinium chloride (CAS No 123-03-5) and thiazoline iodide (CAS No 15764-48-1) and mixtures thereof.
  • Preferred QUATS are the benzalkonium chlorides containing Cs -is-alkyl radicals, in particular C 2 -i 4 alkyl benzyldimethylammonium chloride.
  • a particularly preferred QAC is
  • Cocospentaethoxymethylammonium methosulfate (INCI PEG-5 Cocomonium Methosulfate, Rewoquat® CPEM).
  • cationic surfactants are in particular anionic surfactants compatible cationic surfactants such as quaternary ammonium compounds, for example
  • Cocospentaethoxymethylammonium methosulfate (INCI: PEG-5 Cocomonium Methosulfate, Rewoquat® CPEM).
  • Polymers suitable as additives are, in particular, maleic acid-acrylic acid copolymer Na salt (Sokalan® CP 5), modified polyacrylic acid Na salt (Sokalan® CP 10), modified polycarboxylate Na salt (Sokalan® HP 25), polyalkylene oxide, modified
  • Heptamethyltrisiloxane (Silwet® L77), polyalkylene oxide, modified heptamethyltrisiloxane (Silwet® L-7608) and polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide segments (polyether blocks)), preferably water-soluble linear
  • Polyethersiloxanes with terminal polyether blocks such as Tegopren® 5840, Tegopren® 5843, Tegopren® 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878.
  • anionic surfactant-compatible and / or cationic surfactant is preferably used or omitted in a particular embodiment of the invention entirely on cationic surfactants.
  • the agent according to the invention may contain one or more active ingredients which have a positive effect on the skin.
  • active ingredients which have a positive effect on the skin.
  • These are understood as meaning those raw materials which bring about a sensory effect, ie a positive skin feel, such as smoother skin or a lower feeling of dryness on the skin, as well as active ingredients with positive biological effects such as skin calming or skin protection.
  • the Skin-positively influencing active substances in the sense of this invention can be, for example, soothing, soothing, smoothing, anti-inflammatory or antioxidant-effective
  • the sensory, the skin feel positive influencing agents in the context of this invention can be divided mainly into two groups, the quaternary polymers and the skin affine refatting agents.
  • the quaternary polymers may be synthetic or natural or modified natural polymers.
  • quaternized protein hydrolysates or partial hydrolysates such as the quaternized wheat protein hydrolyzate sold by BASF under the trade name Gluadin® WQ, can be used to improve the feel on the skin.
  • an acrylamide-diallyldimethylammonium chloride copolymer (INCI:
  • Polyquaternium-7) as described e.g. from the company BASF under the trade name Polyquart® 701 / NA, or a copolymer of hydroxyethyl cellulose and
  • Diallyldimethylammonium chloride units such as Celquat® L200 (Akzo Nobel), called.
  • Other copolymers synthesized from several monomers are also suitable active agents, such as those from subunits of AMPS (2-acrylamido-2-methylpropanesulfonic acid), MAPTAC (3- [methacrylamidopropyl] trimethylammonium chloride), DMAPMA (N- [3-dimethylamino] propyl-methacrylamide) and acrylamide compounds
  • Trimethylammonium substituted epoxides (2-Hydroxyethylcellulose 2- [2-hydroxy-3- (trimethylammonio) propoxy] ethyl 2-hydroxy-3- (trimethylammonio) propyl ether chloride, INCI:
  • Polyquaternium-10 for example, available under the trade names Jellner® QH300 (Daicel) or Ucare® Polymer (Dow Amerchol) are also suitable.
  • the usable modified natural polymers further include cationically modified polysaccharides and in particular cationically modified polygalactomannans.
  • Quaternized guar gum which is available, for example, from BASF under the trade name Cosmedia® Guar C 261 N or from Hercules Aqualon under the trade name N-Hance®, may be mentioned here in particular.
  • the skin-affine moisturizing agents are, for example, nourishing wax dispersions. As such, all wax dispersions used in skin care and hair care / conditioning cosmetic preparations can be used.
  • conditioning and conditioning agents used in cosmetic products are also used, such as the conditioner marketed by Evonik under the trade name Amilan® GST 40, which is a mixture of a C12-14 fatty alcohol polyglycol ether with 3 ethylene oxide (EO). Units (INCI: Laureth-3) and one
  • Suitable skin-affinity jerk-greasing active ingredients are mixtures of longer-chain alcohols and ethers, for example the mixture of dicapryl ether and lauryl alcohol available under the trade name Cetiol® LDO from BASF.
  • Polymers such as polypropylene terephthalate sold under the trade name Aristoflex® PEA / PEA 70 by Clariant, or long-chain glycols, such as the polyglycol 35000S from Clariant, a polyethylene glycol (INCI: PEG-800), can also be used as sensory agents in the context of this invention .
  • Protein hydrolysates or partial hydrolysates can also be used in agents according to the invention, for example collagen partial hydrolysates or also vegetable protein partial hydrolysates and also
  • Protein hydrolyzate fatty acid condensates are also suitable. Also suitable are amino acids and
  • Amino acid derivatives such as creatine, the z. B. under the trade name Tego® Cosmo C 100 from Evonik is available.
  • the sensory active substances are preferably present in amounts of from 0.01 to 8% by weight, preferably from 0.1 to 5% by weight, in particular from 1 to 3% by weight.
  • the agent according to the invention in a preferred embodiment additionally contains one or more active substances with positive biological effects.
  • active substances include, for example, plant extracts and vitamins, but also bisabolol, allantoin or A.H.A. complexes.
  • Preferred plant extracts are preferably selected from the group comprising calendula extract (Calendula officinalis), green tea extract, almond extract, arnica extract (Arnica montana), hops extract (Humulus lupulus), balm extract (Melissa officinalis), gentian extract (Gentiana lutea),
  • the plant extracts are preferably used in amounts of 0.01 to 20% by weight, more preferably 0.1 to 5% by weight.
  • vitamins are selected from the group comprising vitamin A (retinol), vitamin B5 (panthenol), vitamin C (ascorbic acid), vitamin E (tocopherol) and mixtures thereof.
  • the vitamins A, C and E act as antioxidants, vitamin A and vitamin E can continue to counteract skin aging, and the panthenol (vitamin B5) has an anti-inflammatory and calming effect.
  • other vitamins such as vitamins B2 (riboflavin) and B12 (cobalamins) or vitamin H (biotin) can be used according to the invention.
  • vitamin B5 and / or vitamin E are particularly preferably used.
  • vitamins are preferably present in amounts of 0.01 to 5% by weight, preferably 0.1 to 3% by weight.
  • the agent according to the invention contains perfumes and / or fragrances. It is possible to use all perfumes and / or fragrances known to the person skilled in the art, with the proviso that they essentially do not adversely affect the properties of the cleaning agent.
  • microcapsules in which these ingredients are stored stable and transport stable and from which they are released to or during use mechanically, chemically, thermally or enzymatically , In a preferred embodiment, therefore, one or more of the skin feel positively affecting agents and / or perfumes and / or fragrances is wholly or partially incorporated into microcapsules.
  • Microcapsules are finely dispersed liquid or solid phases coated with film-forming polymers, in the course of which the polymers are produced after emulsification and coacervation or
  • the active ingredient is shell-shaped enveloped by a solid membrane (microcapsule in the strict sense) or enclosed by a matrix (microsphere or sphere).
  • microcapsule is used in a summarized sense for both variants.
  • Such capsules are usually microscopic ( ⁇ 50 pm) and are sometimes called nanocapsules or Nanospheres are called, they can be dried like powder.
  • larger capsules or pearls visible to the naked eye (> 0.5 mm) filled with active ingredients can also be produced.
  • microcapsules it is possible to use all surfactant-stable capsules and capsule materials or spheres and spheroidal materials available on the market, such as, for example, Primasphere® (chitosan and agar or carboxymethylcellulose) and Primasponge® (alginate, chitosan, agar) from BASF, Hallcrest Microcapsules® (gelatin, gum arabic) from Hallcrest, Inc.
  • Primasphere® chitosan and agar or carboxymethylcellulose
  • Primasponge® alginate, chitosan, agar
  • Hallcrest Microcapsules® gelatin, gum arabic
  • the microcapsules may have any shape in the production-related framework, but they are preferably egg-shaped or ellipsoidal or in particular approximately spherical. Depending on the active ingredient and application, the diameter along its greatest spatial extent may be between 100 nm (not visually recognizable as a capsule) and 10 mm. The preferred diameter is in the range between 0.1 mm and 7 mm, particularly preferred are microcapsules with a diameter between 0.4 mm and 5 mm. To improve the appearance can also dyes, pigments or
  • the release of the active ingredient from the microcapsules can be done mechanically both by grinding the microcapsules during the cleaning process as well as by breaking up by means of a suitable metering device.
  • Other options are the release of the active ingredient by changing the temperature (introduction into warm rinsing water), by shifting the pH value, changing the electrolyte content, etc.
  • microcapsules are used, their content is usually from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, in particular from 0.2 to 3% by weight and most preferably from 0.3 to 2% by weight -%, wherein the inventive agent exclusively similar
  • Microcapsules or else mixtures of different types of microcapsules may contain
  • composition according to the invention may comprise one or more additives from the group of polymers and builders (builders), usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight %, in particular 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, most preferably 0.5 to 1.5% by weight, for example 1% by weight.
  • builders usually in an amount of 0.001 to 5% by weight, preferably 0.01 to 4% by weight %, in particular 0.1 to 3% by weight, more preferably 0.2 to 2% by weight, most preferably 0.5 to 1.5% by weight, for example 1% by weight.
  • Builders suitable as additives are in particular polyaspartic acid sodium salt, ethylenediaminetriacetate cocoalkylacetamide (RewopoKD CHT 12), methylglycinediacetic acid tri-Na salt (Trilon® ES 9964) and acetophosphonic acid (Turpinal® SL).
  • the preferred viscosity for the composition of the invention is 20 ° C and a shear rate of 30 min -1 - measured by a viscometer type Brookfield LV DV II and spindle 31 - in the range of 10 to 5000 mPa s, preferably 50 to 2000 mPa s , in particular 500 to 1500 mPa s, particularly preferably 600 to 1000 mPa s.
  • the viscosity of the composition according to the invention can be increased - in particular with a low surfactant content of the composition - by thickening agents and / or - especially with a high surfactant content of the composition - can be reduced by the water-soluble inorganic salts contained and by solvents.
  • composition according to the invention may additionally comprise one or more polymers
  • polymeric thickeners are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homo- and copolymerates 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, eg. B.
  • propoxylated guar and their mixtures.
  • Other polysaccharide thickeners such as starches or cellulose derivatives, may be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g. Hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropylmethyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • starches of various origins and starch derivatives e.g. Hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropylmethyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • a preferred polymeric thickener is the microbial anionic heteropolysaccharide xanthan gum, that of Xanthomonas campestris and some other species under aerobic Conditions having a molecular weight of 2-15 * 10 ® is produced and is available, for example, from Kelco under the trade name Keltrol®, for example as a cream-colored powder Keltrol® T (transparent) or as white granules Keltrol® RD (Readily Dispersable).
  • Another preferred polymeric thickening agent is the microbial heteropolysaccharide gellan gum, which is formed under aerobic conditions, for example, from Auromonas elodea and especially from Sphingomonas paucimobilis strains.
  • Gellan Gum can be obtained under the trade name Kelcogel® in various qualities from Kelco
  • Acrylic acid polymers suitable as polymeric thickeners are, for example
  • polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene, crosslinked homopolymers of acrylic acid (INCI: Carbomer), which are also referred to as carboxyvinyl polymers.
  • acrylic acid INCI: Carbomer
  • Such polyacrylic acids are i.a. from the Fa.
  • Lubrizol available under the trade name Carbopol®, eg Carbopol® 940 (molecular weight about 4,000,000 g / mol), Carbopol® 941 (molecular weight about 1,250,000 g / mol) or Carbopol® 934 (molecular weight about 3,000,000 g / mol).
  • Carbopol® 940 molecular weight about 4,000,000 g / mol
  • Carbopol® 941 molecular weight about 1,250,000 g / mol
  • Carbopol® 934 molecular weight about 3,000,000 g / mol
  • 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 formed with Ci 4-alkanols, esters, which include for instance the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are available, for example, from Dow under the trade names Aculyn® and Acusol®, eg anionic non-associative ones Polymers Aculyn® 33 (crosslinked), Acusol® 810 and Acusol® 830 (CAS 25852-37-3), (ii) crosslinked high molecular weight acrylic acid copolymers, such as those with an allyl ether of sucrose or pentaerythritol cross-linked copolymers of Cio so-alkyl acrylates with one or more monomers
  • the content of polymeric thickener is usually not more than 8% by weight, preferably between 0.1 and 7% by weight, more preferably between 0.5 and 6% by weight, in particular between 1 and 5% by weight 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 their salts may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, as described e.g. available under the trade name Sokalan® DSC.
  • the use is advantageously carried out in amounts of 0.1 to 8% by weight, preferably 0.5 to 7% by weight, in particular 1, 3 to 6% by weight and particularly preferably 2 to 4% by weight.
  • a change in the dicarboxylic acid (salt) content can - especially in amounts above 2 wt contribute to a clear solution of the ingredients. Also, within certain limits, influencing the viscosity of the mixture by this means is possible. Furthermore, this component influences the solubility of the mixture. This component is particularly preferably used at high surfactant contents, in particular at surfactant contents above 30% by weight. However, if it is possible to dispense with their use, the agent according to the invention is preferably free from dicarboxylic acid (salts).
  • one or more further customary additives in particular in hand dishwashing detergents and hard surface cleaners, can be used, in particular UV stabilizers,
  • AGS of Fa. BASF or mixtures containing this, for example the Euperlane® Fa. BASF, or else styrene-acrylate copolymers, for example Acusol OP 301 or Opulyn 301 Fa. Dow), dyes, corrosion inhibitors, preservatives (eg the technical also referred to as Bronopol 2-bromo-2-nitropropane-1, 3-diol (CAS 52-51-7), which is commercially available, for example, as Myacide® BT from BASF, organic salts, disinfectants, enzymes and pH - Adjusting agent, in amounts of usually not more than 5 wt be included.
  • PH value e.g the technical also referred to as Bronopol 2-bromo-2-nitropropane-1, 3-diol (CAS 52-51-7), which is commercially available, for example, as Myacide® BT from BASF, organic salts, disinfectants, enzymes and pH - Adjusting agent, in amounts of usually not more than 5 wt
  • 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 8, preferably 4.5 to 7, in particular 5 to 6, is preferred.
  • the composition according to the invention may contain one or more buffer substances, usually in amounts of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, in particular 0.01 to 2% by weight. , particularly preferably 0.05 to 1% by weight, most preferably 0.1 to 0.5% by weight, for example 0.2% by weight.
  • buffer substances which are at the same time complexing agents or even chelating agents.
  • Especially preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate 2 * ⁇ iiO and tripotassium citrate H2O.
  • the agent according to the invention can be produced by stirring the individual components together in any order.
  • the order of attachment is not critical to the preparation of the agent.
  • water, surfactants, active ingredients and optionally further of the aforementioned ingredients are stirred together. If perfume and / or dye are used, then their addition to the resulting solution. Subsequently, the pH is adjusted as described above.
  • composition according to the invention can be used for cleaning hard surfaces, in particular for manual cleaning of dishes.
  • the agent according to the invention can be metered from a commercially available bottle for washing.
  • that can be metered from a commercially available bottle for washing.
  • Composition according to the invention also be applied in the form of a foam either directly to the surface to be cleaned or on a sponge, a cloth, a brush or another, optionally moistened, cleaning aid.
  • a manually activated foam dispenser in particular selected from the group comprising aerosol spray dispenser, even pressure-building spray dispenser,
  • Pump spray dispensers and trigger spray dispensers in particular pump foam dispensers, such as those offered by the company Airspray, the company Taplast, the company Keltec or the Daiwa Can Company.
  • pump spray dispensers and trigger spray dispensers with a polyethylene, polypropylene or polypropylene container are also suitable
  • the spray head is preferably equipped with a foam nozzle.
  • the agent can also with the addition of a suitable propellant (eg n-butane, a propane / butane mixture, carbon dioxide, nitrogen or a C0 2 / N 2 mixture) in a corresponding propellant (eg n-butane, a propane / butane mixture, carbon dioxide, nitrogen or a C0 2 / N 2 mixture) in a corresponding
  • a suitable propellant eg n-butane, a propane / butane mixture, carbon dioxide, nitrogen or a C0 2 / N 2 mixture
  • Aerosol spray bottle to be filled
  • a spray dispenser is less preferred. If the agent is to be dosed as a foam, it is necessary in any case to set a suitable viscosity so that the agent can be conveyed through the spray dispenser.
  • All% data are based on wt .-% of active substance, wherein water is made up to 100 wt .-%.
  • the pH of these compositions is 5.5.
  • the storage stability was determined in a so-called challenge test (Preservative Challenge Test).
  • the product sample to be examined for its microbiological stability is inoculated with defined organisms and a count of the living microorganisms is carried out at defined time intervals.
  • the defined organisms are those standard bacteria (bacteria and fungi) that are used according to various international standards, as well as additional strains that are relevant in the context of microbiologically sensitive products. The compatibility of different strains
  • the mixture of bacteria and fungi is added to the product sample and then the germ reduction is determined over time.
  • the germ count in the product sample for example, 0, 7, 14, 21 and 28 days, if necessary, also checked 35 days after inoculation.
  • a reduction in the number of bacteria by four to five log-io stages is sought.
  • compositions according to the invention have similar good stabilizing properties, in particular storage stability, as systems containing isothiazolinone-based preservatives.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne des produits de nettoyage aqueux liquides comprenant : a) au moins un tensioactif ; b) au moins un sel de l'acide sorbique ou des mélanges de celui-ci ; c) au moins un composé choisi parmi l'alcool benzylique, le 2-phényléthanol, le 2-phénoxyéthanol, le 3-phénoxypropanol, le 1-phénoxypropan-2-ol, le 3-phénoxypropan-1,2-diol, le benzyloxyméthanol ou des mélanges de ceux-ci ; d) des additifs et des adjuvants ; et e) de l'eau, la somme de a) à e) s'élevant à 100 % en poids. L'invention concerne également un procédé pour fabriquer lesdits produits et l'utilisation d'un mélange constitué d'au moins un sel de l'acide sorbique ou de mélanges de celui-ci et d'au moins un composé choisi parmi l'alcool benzylique, le 2-phényléthanol, le 2-phénoxyéthanol, le 3-phénoxypropanol, le 1-phénoxypropan-2-ol, le 3-phénoxypropan-1,2-diol, le benzyloxyméthanol ou des mélanges de ceux-ci, afin d'augmenter la stabilité au stockage des produits de nettoyage aqueux liquides.
EP19704771.5A 2018-03-01 2019-02-07 Conservation sans isothiazolinones de produits de nettoyage Pending EP3759205A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102018203111.8A DE102018203111A1 (de) 2018-03-01 2018-03-01 Isothiazolinon-freie Konservierung von Reinigungsmitteln
PCT/EP2019/052963 WO2019166203A1 (fr) 2018-03-01 2019-02-07 Conservation sans isothiazolinones de produits de nettoyage

Publications (1)

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EP3759205A1 true EP3759205A1 (fr) 2021-01-06

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EP (1) EP3759205A1 (fr)
DE (1) DE102018203111A1 (fr)
WO (1) WO2019166203A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11905494B2 (en) * 2020-02-10 2024-02-20 Celanese International Corporation Fabric detergent formulation
CN113278979B (zh) * 2021-04-30 2023-04-11 厦门普诺尔新材料科技有限公司 一种磁力研磨清洗剂及其制备方法
EP4541876A1 (fr) 2023-10-19 2025-04-23 Dalli-Werke GmbH & Co. KG Composition détergente liquide sans conservateur

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GB0112567D0 (en) * 2001-05-24 2001-07-18 Cussons Int Ltd Bactericidal liquid detergent composition
US20080166313A1 (en) * 2005-11-01 2008-07-10 Juice Beauty Compositions for juice-based skin cleansers
DE102006049673A1 (de) 2006-10-18 2008-04-24 Henkel Kgaa Handgeschirrspülmittel mit verbesserter Ölsolubilisierung
CN103784484B (zh) * 2014-01-24 2016-05-11 河南科技大学 一种狗用去势液及其制备方法

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DE102018203111A1 (de) 2019-09-05

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