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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating compositions
• • 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
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

• the invention relates to a washing, cleaning or rinsing agent containing surfactant (s) and a
• the invention also relates to processes for the preparation of the washing, cleaning or rinsing agent and its use.
• the laundry is usually washed by hand or by simple toploader washing machines with short washing times (around 12 minutes).
• hand washing or using the simple Toploader washing machines a strong and long-lasting foaming is desired, because the cleaning performance of a washing, cleaning or rinsing agent is judged by many users on the basis of the visible foam.
• Foaming compounds so-called “foam boosters” are added to washing, cleaning or rinsing agents in order to achieve adequate foaming and foam stability.
• EP 1739161 A1 discloses, for example, the use of alkyl ether carboxylates as foam-promoting compounds usually by alkoxylation and subsequent
• Fatty acid soaps such as coconut fatty acid soaps, oleic acid soaps or tallow fatty acid soaps have always been used as detergents in washing, cleaning or rinsing agents in the form of their sodium or potassium salts.
• these fatty acid soaps are known to have a negative effect on the foaming behavior and are therefore also used as foam regulators.
• the hydroxycarboxylic acid salt of a chaotropic cation has foam-promoting, in particular foam-stabilizing, action.
• the salts are readily available by reacting hydroxycarboxylic acid with a corresponding base.
• hydroxycarboxylic acid is selected from the group of saturated
• Hydroxyfatty acids unsaturated hydroxyfatty acids and mixtures thereof. It is particularly preferred that the hydroxycarboxylic acid is 12-hydroxystearic acid and / or ricinoleic acid.
• the use of hydroxy fatty acids as foam-promoting compounds is particularly advantageous in terms of sustainability, since these are based on renewable raw materials.
• the chaotropic cation is selected from the group consisting of Al 3+ , Mg 2+ , Ca 2+ , Ba 2+ , alkylammonium cations, alkanolammonium cations, glucammonium cations,
• the chaotropic cation is selected from the group consisting of alkylammonium cations, alkanolammonium cations, guanidinium cations, and mixtures thereof.
• amine-based bases such as alkylamines, alkanolamines or guanidine
• the hydroxycarboxylic acid salt of a chaotropic cation can be obtained via a simple acid-base reaction.
• the invention relates to the use of a hydroxycarboxylic acid salt of a chaotropic cation in a washing, cleaning or rinsing agent for increasing the foam stability of the washing,
• the invention relates to a process for producing a washing, cleaning or rinsing agent containing 1 to 70 wt .-%, based on the total washing, cleaning or rinsing agent, surfactant (s) and 0.1 to 10 wt .-%, based on the total washing, cleaning or rinsing agent, hydroxycarboxylic acid salt of a chaotropic cation, in which
• the resulting salt is mixed with the surfactants and the further constituents of the washing, cleaning or rinsing agent.
• the washing, cleaning or rinsing agent contains surfactant (s) and the hydroxycarboxylic acid salt of a chaotropic cation.
• the hydroxycarboxylic acid can be selected from:
• the hydroxycarboxylic acid is preferably selected from the saturated and / or unsaturated hydroxy fatty acids.
• the hydroxycarboxylic acid is preferably selected from 12-hydroxystearic acid, ⁇ -hydroxyoctadecanoic acid, 14-hydroxyeicosenoic acid, leucic acid, 2-ethyl-3-hydroxycaprylic acid,
• Ricinoleic acid 3-hydroxy-4-hexanoic acid, hydroxynervonic acid, 16-hydroxy-6-hexadecenoic acid, 9, 10-dihydroxyoctadecanoic acid, 9, 12-dihydroxyoctadecanoic acid, aleuritic acid, 9, 10, 12-trihydroxyoctadecanoic acid, hexahydroxyoctadecanoic acid, octahydroxyoctadecanoic acid and mixtures thereof.
• the hydroxycarboxylic acid is most preferably selected from the unsaturated hydroxy fatty acids having 16 to 20 carbon atoms, preferably 18 carbon atoms.
• the hydroxycarboxylic acid used is particularly preferably 12-hydroxystearic acid or ricinoleic acid.
• the hydroxycarboxylic acid is present in neutralized, ie anionic form and has a chaotropic cation as counterion.
• Chaotropic is the term for the property of substances that destroy regular structure of liquid water based on the formation of hydrogen bonds.
• Suitable chaotropic cations include, for example, Al 3+ , Mg 2+ , Ca 2+ , Ba 2+ , alkylammonium cations, alkanolammonium cations, glucammonium cations, guanidinium cations, and mixtures thereof.
• alkylammonium cations alkanolammonium cations, guanidinium cations and mixtures thereof as chaotropic cations in the washing, cleaning or rinsing agents.
• Particularly preferred chaotropic cations include trimethylammonium cations,
• Triethylammonium cations 2-hydroxyethyl-dimethylammonium cations, monoethanolammonium cations, diethanolammonium cations, triethanolammonium cations and / or guanidinium cations.
• the hydroxycarboxylic acid is reacted with a base containing a chaotropic cation or the unprotonated form of the chaotropic cation.
• a base containing a chaotropic cation or the unprotonated form of the chaotropic cation.
• the hydroxycarboxylic acid is neutralized with an equimolar amount of base. The neutralization preferably takes place in the liquid phase.
• the hydroxycarboxylic acid salt of a chaotropic cation can be used directly in the form of the resulting reaction mixture.
• the amount of hydroxycarboxylic acid salt of a chaotropic cation is preferably 0.5 to 8 wt .-%, and more preferably 2 to 5 wt .-%, each based on the total washing, cleaning or rinsing agent.
• the washing, cleaning or rinsing agent further contains a surfactant which may be, for example, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a cationic surfactant or a mixture thereof.
• a washing or cleaning agent preferably contains anionic and nonionic surfactant.
• a rinse preferably contains anionic surfactant and amphoteric surfactant.
• the anionic surfactant used may preferably be sulfonates and / or sulfates.
• the surfactants of the sulfonate type are preferably C 9 . 13- Alkylbenzolsulfonate, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates 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 acid hydrolysis of the sulfonation, into consideration , Also suitable are C 2 -i8-alkanesulfonates and the esters of ⁇ -sulfofatty acids (ester sulfonates), for example, the ⁇ -sulfonated Methylester of hydrogenated coconut, palm kernel or tallow fatty acids.
• the Ci 2 -Ci 6 alkyl sulfates and Ci 2 -Ci 5 - alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
• 2,3-alkyl sulfates are also suitable anionic surfactants.
• fatty alcohol ether sulfates such as 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 Ci 2 _i 8 -Fettalkohole with 1 to 4 EO, are suitable.
• EO ethylene oxide
• Ci 2 _i 8 -Fettalkohole with 1 to 4 EO are suitable.
• C 2 -C 4 -fatty alcohol ether sulfates with 2 EO.
• Suitable anionic surfactants are soaps. Suitable are saturated and unsaturated
• Fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
• the anionic surfactants including the soaps may be in the form of their sodium or potassium salts.
• anionic surfactants which can be used in particular in hand dishwashing detergents are
• Monoglyceride sulfates and ester sulfonates (sulfo fatty acid esters), lignosulfonates, fatty acid cyanamides, sulfosuccinates, sulfosuccinamates and sulfosuccinamides, imidosuccinate, fatty acid isethionates,
• Alkyl (ether) phosphates Alkyl (ether) phosphates.
• anionic surfactants include, in particular C 9 .i 3 alkyl benzene sulfonates, fatty alcohol ether sulfates and soaps.
• anionic surfactants preferably used in particular in hand dishwashing detergents are, in particular, fatty alcohol ether sulfates and alkyl sulfonates.
• the content of anionic surfactant including soaps is preferably 2 to 40% by weight and more preferably 5 to 30% by weight, based in each case on the entire washing, cleaning or rinsing agent.
• Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof.
• the nonionic surfactant used is preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
• alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred.
• EO ethylene oxide
• ethoxylated alcohols include, for example, Ci 2 -i4-alcohols with 4 EO or 7 EO, Cg-n-alcohol with 7 EO, C-i3-i5 alcohols with 5 EO, 7 EO or 8 EO, Ci 2 -i8 alcohols with 5 EO or 7 EO and mixtures of these.
• the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these
• Nonionic surfactants can also be used fatty alcohols with more than 12 EO. 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 -i8-fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
• the washing, cleaning, Aftertreatment or washing aids a Ci 2 -i 8-fatty alcohol with 7 EO or a Ci 3 .i 5 -oxo-alcohol with 7 EO or 8 EO as nonionic surfactant.
• the content of nonionic surfactant is preferably 1 to 40 wt .-% and more preferably 2 to 30 wt .-%, each based on the total washing, cleaning or rinsing agent.
• Suitable amphoteric surfactants which are mainly used in hand dishwashing detergents, are betaines such as alkylbetaines, alkylamidobetaines, imidazolinium betaines, sulfobetaines or phosphobetaines, alkyl-substituted amino acids and acylated amino acids.
• the surfactants are
• the surfactants a) fatty alcohol ether sulfates and b) C 9 .i 3 -alkylbenzenesulfonates, preferably in a ratio a): b) of 1: 2 to 1: 8, are present.
• Particularly preferred cationic surfactants are quaternary ammonium compounds, so-called "QACs".
• the total amount of surfactant in a washing, cleaning or rinsing agent is up to 70 wt .-%, preferably up to 50 wt .-%, based on the total washing, cleaning or rinsing agent.
• the washing, cleaning or rinsing agent may contain other ingredients that further improve the performance and / or aesthetic properties of the washing, cleaning or rinsing agent.
• the washing, cleaning or rinsing agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, Foam inhibitors, silicone oils, inlet preventer, anti-crease agents,
• Antioxidants preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, skin-care agents, swelling and anti-slip agents, additives for improving the drainage and drying behavior, disinfectants, softening agents
• UV absorbers Components as well as UV absorbers.
• the washing, cleaning or rinsing agents are preferably liquid and can water as
• the washing, cleaning or rinsing agents may contain non-aqueous solvents. If the washing, cleaning or rinsing agents are solid, they may contain neutral fillers such as sodium sulfate or sodium carbonate.
• the detergents or cleaners can be used for washing and / or cleaning textile fabrics.
• the rinsing agents can be used to clean hard surfaces, especially dishes.
• the hydroxycarboxylic acid salt of a chaotropic cation is preferably used to increase the
• Foam stability used in a washing, cleaning or rinsing agent Foam stability used in a washing, cleaning or rinsing agent.
• One possibility for the preparation of a liquid washing, cleaning or rinsing agent involves first the hydroxycarboxylic acid salt of a chaotropic cation by neutralization of the
• Hydroxycarboxylic acid is prepared with a corresponding base. Subsequently, the resulting mixture is transferred to a stirred tank and water, non-aqueous solvents and the other surfactants, if present, added. Then, if present, the fatty acid is added and saponification of the fatty acid moiety occurs at 50 to 60 ° C. Subsequently, the other ingredients, preferably in portions added.
• the hydroxycarboxylic acid salt of a chaotropic cation can be detected only at the end of the
• a solid washing, cleaning or rinsing agent is prepared by known processes, which may comprise, for example, drying steps, mixing steps, densification steps, shaping steps and / or the subsequent addition of heat-sensitive ingredients ("post-addition") In a suitable mixing step, further compaction and / or shaping steps may follow to produce detergent tablets.
• compositions of three washing, cleaning or rinsing agents E1 to E3 according to the invention and the compositions of two are not
• Enzymes (cellulase, amylase & 0.8-0.4-0.4
• Foam volume (stated in ml) as a function of time.
• the improved foam stability of the washing, cleaning or rinsing agents according to the invention is presumably based on the formation of tubular structures in the washing solution.
• These tubular structures consist of the hydroxycarboxylic acid salt of a chaotropic cation and are independent of the parallel surfactant system. These tubular structures increase the stability of the foam lamellae and thus of the entire foam.

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

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Citations (10)

• 2012
  • 2012-04-24 DE DE201210206707 patent/DE102012206707A1/de not_active Withdrawn
• 2013
  • 2013-04-22 EP EP13718185.5A patent/EP2841544A1/fr not_active Withdrawn
  • 2013-04-22 WO PCT/EP2013/058320 patent/WO2013160265A1/fr not_active Ceased

Patent Citations (10)

Non-Patent Citations (3)

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