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
  • C11D1/38—Cationic compounds
  • C11D1/645—Mixtures of compounds all of which are cationic
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated

Definitions

• the invention relates to surfactant mixtures of fatty acid N-alkyl polyhydroxyamides and fatty acid amido alkoxylates, as well as detergents and cleaning agents, these Contain surfactant mixtures.
• fatty acid N-alkyl polyhydroxyamides especially of Fatty acid N-methylglucamide in detergents and cleaning agents is already known (WO 92/06 159, WO 920/6160).
• fatty acid N-alkyl-polyhydroxyalkylamides are their high Cleaning power, good fat dispersibility, good skin friendliness, their good biodegradability and its production from renewable raw materials.
• fatty acid amido alkoxylates to fatty acid polyhydroxyamides has the effect also a decrease in viscosity and affects the cold cloud point Cheap.
• the invention relates to surfactant mixtures of fatty acid N-alkyl polyhydroxyamides of the formula I.
• Z is a polyhydroxy hydrocarbon group with at least three hydroxyl groups, which may also be alkoxylated, and R 2 C 1 -C 8 alkyl, a group of the formulas - (CH 2 ) x NR 3rd R 4 or R 5 O (CH 2 ) n -, where R 3 and R 4 are C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl, R 5 C 1 -C 4 alkyl, n is a number 2 to 4 and x represent a number from 2 to 10 and fatty acid amido alkoxylates of the formula II R-CON (R 6 ) (R 7 ) wherein R is an alkyl group or alkenyl group with 7 to 21 carbon atoms, R 6 is hydrogen or a group - (AO) x H, R 7 is a group - (AO) x H, A is a group of the formulas -C 2 H 4 -, -C 3 H 6 - or -C 4
• R 1 is C 7 -C 21 -alkyl or C 7 -C 21 -alkenyl.
• the R 1 CO radical can be, for example, the acyl radical of coconut fatty acid, stearic acid, oleic acid, lauric acid, myristic acid, capric acid, palmitic acid or tallow fatty acid.
• R 2 is preferably C 1 -C 4 alkyl and Z is preferably a polyhydroxyalkyl radical with 3 to 5 C atoms, which is derived from sugar alcohols, for example 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1- Deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriityl.
• C 8 -C 22 in particular C 12 -C 18 acyl-N-methylglucamides, are particularly preferred.
• the compounds of the formula I are prepared in a manner known per se by reductive amination of a reductive sugar with an alkylamine and subsequent esterification with a fatty acid or fatty acid ester. More about The preparation of these compounds can be found in WO 92/06160 and there specified literature.
• Preferred fatty acid amidoalkoxylates of the formula II are compounds of the formula II in which RC 9 -C 17 -alkyl, R 6 is hydrogen and R 7 is a group of the formula - (AO) x H and A -C 2 H 4 - or -C 3 H 6 - mean.
• Fatty acid amido alkoxylates of the formula II are obtained by reacting Fatty acid methyl ester and mono- or dialkanolamine and subsequent Receive alkoxylation.
• the preparation of the surfactant mixtures according to the invention containing fatty acid N-alkyl polyhydroxyamide and fatty acid amido alkoxylate is carried out in the following way: Solid to highly viscous fatty acid N-alkyl polyhydroxyamide is heated to temperatures heated from 40 ° C to 130 ° C, preferably 50 ° C to 100 ° C, the Fatty acid amido alkoxylate is added and at these temperatures Kneading in the period from 0.5 minutes to 180 minutes, preferably 1 to 30 minutes intimately mixed.
• washing and Cleaning agents and dishwashing detergents such as conventional additives Surfactants, solubilizers, defoamers, builders, carrier materials, salts and Adjusting agents, bleaching agents, optical brighteners, graying inhibitors and Bleach activators can be processed further.
• the weight ratio of the fatty acid polyhydroxyamides of the formula I and Fatty acid amido alkoxylates of the formula II can vary within wide limits is generally 90:10 to 10:90, preferably 90:10 to 30:70, in particular 80:20 to 50:50% by weight.
• the surfactant mixtures according to the invention can generally be found in all washing and Use cleaning agents of all kinds, preferably these are used Surfactant mixtures for the manufacture of hand dishwashing liquids All-purpose cleaners or liquid detergents for hand washing. All these Detergents and cleaning agents can be used in addition to those according to the invention Surfactant mixtures and other non-ionic, anionic, cationic surfactants or amphoteric in nature as well as customary auxiliaries and additives in different Amounts included.
• Preferred nonionic surfactants are fatty alcohol oxyethylates with approx. 1 to approx. 25 mol ethylene oxide.
• the alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms.
• the condensation products of alcohols which contain an alkyl chain of 10 to 20 carbons with 2 to 18 mol of ethylene oxide per mol of alcohol are particularly preferred.
• the alkyl chain can be saturated or unsaturated.
• the alcohol ethoxylates can also have a narrow homolog distribution of the ethylene oxide ( Narrow Range Ethoxylates ”) or a broad homolog distribution of ethylene oxide ( Broad Range Ethoxylates ").
• nonionic surfactants of this type are Tergitol TM 15-S-9 (condensation product of a C11-C15 linear secondary alcohol with 9 mol ethylene oxide), Tergitol TM 24-L-NMW (condensation product of a C12- C14-linear primary alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution).
• Genapol TM brands from Clariant GmbH also fall under this product class.
• nonionic surfactants in question such as polyethylene, polypropylene and Polybutylene oxide adducts of alkylphenols with 6 to 12 carbon atoms in the alkyl chain, Addition products of ethylene oxide with a hydrophobic base formed from the Condensation of propylene oxide with propylene glycol or addition products from Ethylene oxide with a reaction product of propylene oxide and ethylenediamine.
• Amine oxides of the formula III are used, wherein R 8 represents an alkyl, hydroxyalkyl or alkylphenol group or mixtures thereof with a chain length of 8 to 22 carbon atoms; R 9 is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; R 10 is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms or a polyethylene oxide group with 1 to 3 ethylene oxide units.
• the R 10 / R 9 groups can be connected to one another via an oxygen or nitrogen atom and thus form a ring.
• These amine oxides particularly include C 10 -C 18 alkyldimethylamine oxides and C 8 -C 12 alkoxyethyl dihydroxyethylamine oxides.
• the surfactant mixtures according to the invention from fatty acid polyhydroxyamides Formula I and the fatty acid amido alkoxylates according to formula II can be more contain nonionic surfactants in a weight ratio of 95 to 5 to 5:95.
• a weight ratio of 80 to 20 to 20 to 80 is advantageous.
• the Mixtures according to the invention also contain anionic surfactants.
• Straight-chain and branched are particularly suitable as anionic surfactants Alkyl sulfates, sulfonates, carboxylates, phosphates, alkyl ester sulfonates, Arylalkyl sulfonates,, alkyl ether sulfates and mixtures of the above Links.
• anionic surfactants Alkyl sulfates, sulfonates, carboxylates, phosphates, alkyl ester sulfonates, Arylalkyl sulfonates, alkyl ether sulfates and mixtures of the above Links.
• anionic surfactants Alkyl sulfates, sulfonates, carboxylates, phosphates, alkyl ester sulfonates, Arylalkyl sulfonates, alkyl ether sulfates and mixtures of the above Links.
• the following are some of the types of anionic surfactants are described in more
• Alkyl ester sulfonates are linear esters of C 8 -C 20 carboxylic acids (ie fatty acids) which are sulfonated by SO 3 , as in The Journal of the American Oil Chemists Society ", 52 (1975), pp. 323-329.
• Suitable starting materials are natural fat derivatives, such as, for example, tallow or palm oil fatty acid.
• Alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, in which R is preferably a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C 12 -C 18 alkyl or Represents hydroxyalkyl.
• R is preferably a C 10 -C 24 hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C 12 -C 18 alkyl or Represents hydroxyalkyl.
• M is hydrogen or a cation, for example an alkali metal cation (for example sodium, potassium, lithium) or ammonium or substituted ammonium, for example a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation such as tetramethylammonium and dimethylpiperidinium cation and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
• Alkyl chains with C 12 -C 16 are preferred for low washing temperatures (eg below approx. 50 ° C) and alkyl chains with C 16 -C 18 are preferred for higher washing temperatures (eg above approx. 50 ° C).
• the alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is an unsubstituted C 10 -C 24 -alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 -alkyl or hydroxyalkyl radical, particularly preferably a C. 12 -C 18 alkyl or hydroxyalkyl.
• A is an ethoxy or propoxy unit
• m is a number greater than 0, typically between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3
• M is a hydrogen atom or a cation such as e.g. a metal cation (e.g.
• substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like.
• C 12 C 18 alkyl polyethoxylate (1.0) sulfate examples which may be mentioned C 12 C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 alkyl polyethoxylate (3.0 ) sulfate, C 12 -C 18 alkyl polyethoxylate (4.0) sulfate, the cation being sodium or potassium.
• anionic surfactants which are useful for use in detergents and cleaning agents are C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in British Patent GB 1,082,179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol alkylphenol ether sulfates, primary paraffinsulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as the acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoester of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinates (
• Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids can also be used. Further examples are in Surface Active Agents and Detergents "(Vol. I and II, Schwartz, Perry and Berch). A large number of such surfactants are also claimed in US Pat. No. 3,929,678.
• the surfactant mixtures according to the invention can contain the anionic surfactants in Weight ratio of 99 to 1 to 1:99 included.
• amphoteric surfactants which can be used in the formulations of the present invention are, in particular, those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be linear or branched and in which one of the aliphatic Contains substituents between 8 to 18 carbon atoms and contains an anionic, water-soluble group such as carboxy, sulfonate, sulfate, phosphate or phosphonate.
• Amphoteric surfactants in this context include amphoteric imidazolinium surfactants as shown in Formula IV below: wherein R 11 is C 8 -C 22 alkyl or alkenyl, preferably C 12 -C 16 , R 12 is hydrogen or a group of the formula CH 2 CO 2 M, R 13 is a group of the formulas CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, R 14 is hydrogen or a group of the formulas CH 2 CH 2 OH or CH 2 CH 2 OCH 2 CHCOOM, Z is CO 2 M or CH 2 CO 2 M, n is 2 or 3, preferably 2, M. Hydrogen or a cation such as alkali metal, alkaline earth metal, ammonia or alkanolammonium.
• R 11 is C 8 -C 22 alkyl or alkenyl, preferably C 12 -C 16
• R 12 is hydrogen or a group of the formula CH 2 CO 2 M
• R 13 is a group of the formulas CH 2 CH 2
• Preferred amphoteric surfactants of the above formula are monocarboxylates and Dicarboxylates. Close examples of these connections Cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, Cocoamphocarboxyglycinat (or also known as Cocoamphodiacetat) and Cocoamphoacetate.
• amphoteric surfactants are alkyldimethylbetaines, Alkylamidobetaines and alkyldipolyethoxybetaines with an alkyl radical which is linear or be branched, with 8 to 22 carbon atoms, preferably with 8 to 18 Carbon atoms and particularly preferably with 12 to 18 carbon atoms. These connections are e.g. from Clariant GmbH under the trade name Genagen® CAB marketed.
• cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid alkanolamine ester salts and Dialkylaminopropylamine ester salts.
• the surfactant mixtures according to the invention can the cationic surfactants in a weight ratio of 99 to 1 to 1:99 contain. A weight ratio of 90 to 10 to 10 to 90 is advantageous.
• the detergents and cleaning agents contain, depending on the application, in addition to mentioned surfactants and the specific auxiliaries and additives for example builders, salts, bleaching agents, bleach activators, optical brighteners, Graying inhibitors, solubilizers, enzymes, thickeners, Preservatives, fragrances and dyes, pearlescent agents, foam inhibitors, Sequestrant.
• Suitable and especially ecological harmless builder substances such as finely crystalline, synthetic water-containing Zeolites of type NaA, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g have a preferred use.
• non-aqueous Systems preferably use layered silicates. Zeolite and the Layered silicates can be contained in an amount of up to 20% by weight.
• Usable organic builders are, for example, those in the preferred form their sodium salts used percarboxylic acids, such as citric acid and Nitriloacetate (NTA), ethylenediaminetetraacetic acid, provided such use ecological reasons is not objectionable.
• polymeric carboxylates and their salts are used.
• the relative molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid, in particular also water-soluble polyacrylates are suitable, for example with about 1% Polyallylethers of sucrose are cross-linked and have a relative molecular weight own over a million. Examples of this are those under the name Carbopol 940 and 941 available polymers.
• the cross-linked polyacrylates are in amounts not exceeding 1% by weight, preferably in amounts of 0.2 to 0.7 wt .-% used.
• These framework substances can be used in amounts of up to 5% by weight.
• the agents according to the invention can be used as foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica.
• foam inhibitors Fatty acid alkyl ester alkoxylates, organopolysiloxanes and their mixtures with microfine, optionally silanized silica as well as paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica.
• foam inhibitors can also be used advantageously, e.g. those made of silicone oil, paraffin oil or waxes.
• the liquid detergents can be used as optical brighteners, for example derivatives of Contain diaminostilbenedisulfonic acid or its alkali metal salts, which are good in let the dispersion work in.
• the maximum amount of brighteners in the Agents according to the invention is 0.5 wt .-%, preferably amounts of 0.02 to 0.25 wt .-% used.
• the desired viscosity of the agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and thickeners.
• organic solvents all monohydric or polyhydric alcohols are suitable as organic solvents.
• Alcohols with 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used.
• Further preferred alcohols are polyethylene glycols with a relative molecular weight below 2000.
• polyethylene glycol with a relative molecular weight between 200 and 600 in amounts of up to 45% by weight and of polyethylene glycol with a relative molecular weight between 400 and 600 in amounts of 5 up to 25% by weight is preferred.
• An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, it being possible for the liquid detergents according to the invention to contain 8 to 12% by weight of such a mixture.
• Suitable solvents are, for example, triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
• Hardened castor oil, salts of long chain fatty acids preferably in amounts of 0 to 5 wt .-% and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, Aluminum, magnesium and titanium stearates or the sodium and / or potassium salts behenic acid and polysaccharides, especially xanthan gum, guar guar, Agar, alginates and tyloses, carboxymethyl cellulose and Hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone.
• Enzymes come from the class of proteases, lipases, amylases or their mixtures in question. Their proportion can be 0.2 to 1% by weight. The enzymes can be adsorbed on carrier substances and / or in coating substances be embedded.
• HEDP 1-hydroxyethane-1,1-diphosphonic acid
• DTPMP Diethylenetriaminepentamethylenephosphonic acid
• Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, pentanediol or sorbic acid.
• pearlescent agents examples include glycol distearic acid esters such as Ethylene glycol distearate, but also fatty acid monoglycol esters into consideration.
• Sodium sulfate, sodium carbonate or sodium silicate (water glass), for example, are used as salts or adjusting agents.
• further additives are sodium borate, starch, sucrose, polydextrose, stilbene compounds, methyl cellulose, toluenesulfonate, cumene sulfonate, soaps and silicones.
• the following tables show the technical advantages of a detergent containing a surfactant mixture according to the invention compared to two analog detergents, each containing only one component of the surfactant mixture according to the invention.
• Composition in% Detergent 1 Detergent 2 Detergent 3 Hostapur SAS 60 16.0 16.0 16.0 Genapol LRO fl.
• the surfactant mixture of fatty acid N-methylglucamide and fatty acid amidooxethylate according to the invention shows a significant improvement in the solubilizing capacity with simultaneous improvement in the foam stability compared to the pure fatty acid N-methylglucamide variant.
• the detergents have a WAS content of 30%, with 27% for a mixture of alkylbenzenesulfonate / ether sulfate or alkyl sulfate / ether sulfate and 3% for the co-surfactant (fatty acid-N-methylglucamide or a mixture of C 12 -C 14 -Fatty acid-N-methylglucamide and coconut fatty acid monoethanolamide with 5 EO in a mixing ratio of 70 to 30) are not required.
• Composition in% Detergent 4 Detergent 5 Detergent 6 Detergent 7 Genapol LRO fl.
• the plate test shows the foam-stabilizing effect of the invention Mixture of surfactants from C12 / 14 fatty acid N-methylglucamide and Coconut fatty acid monoethanolamide with 5 EO in a mixing ratio of 70 to 30.
• STIWA I and STIWA II are soils with the following composition: STIWA I STIWA II Beef tallow 1.375% 4.125% butter 1.375% 4.125% Creme fraiche Cheese 1.375% 4.125% lard 1.375% 4.125% margarine 1.375% 4, 125% olive oil 1,375 4.125% Palmin 1,375 4.125% Sunflower oil 1.375% 4.125% Drinking water 45% 45% Rye flour 33% 17% Milk powder 11% 5% dye 0.2% 0.2% Some formulations using the surfactant mixture according to the invention are described in more detail below.

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• Chemical Kinetics & Catalysis (AREA)
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• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Cosmetics (AREA)

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• 1999
  • 1999-08-24 DE DE19940116A patent/DE19940116A1/de not_active Withdrawn
• 2000
  • 2000-08-11 EP EP00117406A patent/EP1078978A1/fr not_active Withdrawn
  • 2000-08-23 BR BR0003766-4A patent/BR0003766A/pt not_active Application Discontinuation
  • 2000-08-23 JP JP2000252535A patent/JP2001131579A/ja not_active Withdrawn

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