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
  • C11D1/66—Non-ionic compounds
  • C11D1/825—Mixtures of compounds all of which are non-ionic
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
  • C11D1/721—End blocked ethers

Definitions

• the present invention relates to the use of selected surface-active substances, alone or in combination, for use in cleaning agents and in particular in dishwashing detergents for automatic dishwashing.
• the cleaning of hard surfaces and especially the washing of dishes makes special demands on the cleaner used.
• the three components of the machine system are cleaner, rinse aid and regeneration salt for water softening.
• the central tasks of the main component cleaners are the soil release, the dirt dispersion, the binding of residual water hardness and the corrosion inhibition.
• An essential parameter for dishwashing is the rinse aid performance. It is determined how large the proportion of deposits on the dishes, after they were rinsed.
• the deposits are essentially mineral compounds, in particular Ca and / or Mg salts, but also surfactant residues. However, lime mainly leads to undesirable deposits for the user.
• common dishwashing agents in particular those for automatic dishwashing, generally contain so-called rinse aid.
• rinse aids usually comprise mixtures of low foaming nonionic surfactants, typically fatty alcohol polyethylene / polypropylene glycol ethers, solubilizers (eg cumene sulfonate), organic acids (eg citric acid) and solvents (eg ethanol) It is to influence the interfacial tension of the water so that it can run in a very thin, coherent film of items to be washed, so that remain in the subsequent drying process no water droplets, stripes or films. There are differences between two types of deposits. On the one hand, the so-called “spotting”, which is caused by drying drops of water, is examined. On the other hand, the "filming”, which are layers that result from the drying of thin water films, is evaluated.
• solubilizers eg cumene sulfonate
• organic acids eg citric acid
• solvents eg ethanol
• combination products are increasingly being used, in which the various functions, such as cleaning, rinsing, water softening and, if appropriate, metal, in particular silver protection or a glass protection function, are combined in a preferably solid form.
• agents are referred to as multifunctional agents.
• so-called 3-in-1 products which combine cleaners, rinse aids and water softening in the form of a solid compact ("tabs"), are found in the market. Due to the increased use of such multifunctional agents but the drying performance has become worse compared to the use of a classic rinse aid. Drying performance is to be understood in how far the cleaned items to be washed, after passing through the dishwashing process, still have water, preferably water drops, on the surface.
• the remaining water on the surface must then either be removed mechanically (eg by dry wiping) or the ware must be allowed to air-dry. The user must wait until the water evaporates.
• residues eg lime and / or surfactant residues or other residues dissolved or dispersed in the water
• residues eg lime and / or surfactant residues or other residues dissolved or dispersed in the water
• the EP 1 306 423 A2 discloses aqueous detergents which contain alkyl ether sulfates and amphoteric glycine compounds and are suitable for improving the drying behavior of dishwashing detergents.
• the DE 100 45 289 A1 describes hand dishwashing detergents which contain certain quaternary ammonium compounds and alkyl ether sulfates side by side and also show a particularly good drying behavior. Furthermore, additives for cleaning agents must not adversely affect the rinsing and in particular the rinse performance of the cleaner. Ideally, an additive should even improve the overall performance of the cleaner.
• the mixtures according to the invention necessarily contain compounds of the type a). These are compounds of the above formulas (Ia) and / or (Ib) wherein certain structures are preferred.
• compounds according to the general formula (Ia) are preferred when M is a CH 2 -CRH group, R is a linear, saturated alkyl radical having 8 to 16, preferably 8 to 12 and in particular 8 to 10 carbon atoms, and R 'and R "each independently represent a linear, saturated alkyl radical having from 10 to 16, preferably 10 to 14, carbon atoms, and n and m independently of one another may have values of from 20 to 30.
• Such compounds may For example, by reacting alkyldiols, HO-CHR-CH 2 -OH are obtained with ethylene oxide followed by a reaction with an Alkylepoxid to close the free OH functions, so that a dihydroxy ether is formed in the sequence.
• the second component of the mixtures are compounds of the formulas (II) and (III), which can be referred to as hydroxy mixed ethers.
• HME Hydroxy mixed ethers
• hydroxy mixed ethers are known from the literature and are described, for example, in the German application DE 19738866 described. They are prepared, for example, by reaction of 1,2-epoxyalkanes (R "CHOCH 2 ), where R" is an alkyl and / or alkenyl radical having 2 to 22, in particular 6 to 16, carbon atoms, with alkoxylated alcohols.
• R'-OH 1,2-epoxyalkanes
• R '-OH having 4 to 18 carbon atoms
• R ' is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, stands.
• Suitable straight-chain alcohols are butanol-1, caproic, eananthic, caprylic, pelargonic, capric alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmityl alcohol, heptadecanol-1, stearyl alcohol, nonadecanol- 1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as obtained in the high pressure hydrogenation of technical methyl esters based on fats and oils.
• branched alcohols examples include so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are prepared by the oxo process and so-called Guerbet alcohols which are branched in the 2-position with an alkyl group.
• Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
• the alcohols are used in the form of their alkoxylates, which are prepared by reaction of the alcohols with ethylene oxide in a known manner.
• R 1 is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, or a radical R 2 is -CH (OH) CH 2 , where R 2 is a linear or branched alkyl and / or Alkenyl radical having 8 to 16 carbon atoms, x represents a number from 40 to 80, and M represents a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms.
• Preferred for the purposes of the invention are those hydroxy mixed ethers derived from ethoxylates of monohydric alcohols of the formula R 1 -OH having 6 to 18 carbon atoms, preferably 6 to 16 and in particular 8 to 10 carbon atoms, wherein R 1 is a linear alkyl radical and x is 40 to 60.
• those compounds of general formula (II) are preferred in which the index x for a Number from 40 to 70, preferably 40 to 60 and in particular from 40 to 50 stands. M is then a hydrogen atom.
• R 1 is an alkyl radical having 8 to 10 carbon atoms, in particular on the basis of a native fatty alcohol
• R 2 is an alkyl radical having 10 carbon atoms, in particular a linear alkyl group
• x 40 to 60 stands.
• R ' is a saturated alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms and R "is an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms
• the index x may have values of from 20 to 80, preferably from 30 to 60 and in particular from 40 to 50, wherein in general those compounds are preferred in which the index x is greater than 40 are preferred.
• Particularly preferred compounds of type b2) are, for example, those in which, in the formula (III), the index y is a number from 20 to 30, preferably from 20 to 25.
• R 3 in the formula (III) represents an alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms
• R 4 is an alkyl radical having 10 to 12, preferably 10 carbon atoms
• y a number from 15 to 35, preferably 20 to 30
• z is a number from 1 to 3, preferably 1 means.
• Preference is also given to mixtures containing as surface-active compound of type b2) a compound of the general formula (III) in which R 3 is an alkyl and / or alkenyl radical having 9 to 18 carbon atoms and R 4 is an alkyl or Alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35.
• mixtures which contain as surface-active compound of type b2) a compound of the general formula (III), in which R 3 is an alkyl and / or alkenyl radical having 8 to 12 carbon atoms and R 4 is an alkyl or Alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35 and z is a number from 1 to 3.
• the compounds of type b2) are also hydroxy mixed ether derivatives which can be prepared by reacting propoxylated and / or ethoxylated fatty alcohols with alkyl epoxides by ring opening in an alkaline medium.
• both a propylene oxide radical CH 2 CHCH 3 O (PO) and an ethylene oxide radical CH 2 CH 2 O (EO) contain, possible that from the direction of the C atom with the free hydroxyl group first the EO residues and then the PO residues are arranged in blocks, whereby the sequence first PO, then EO possible is.
• the alkoxide groups can also be randomly distributed (randomized) in the molecule. It is also possible to use both block and random alkoxylates side by side.
• the values are average values since, due to their production, different alkoxylated derivatives are present side by side.
• the number of alkoxide groups can therefore also be odd.
• HME of the general formula (III) is described by the following Markush formula: where R ' and R "independently of one another represent a saturated alkyl radical having 8 to 12, preferably 8 to 10, carbon atoms.
• the present invention now makes use of the finding that the presence of selected HME (type b)), or their derivatives, in combination with structure-different surface-active compounds of type a) advantageous drying and / or rinsing performance of cleaner formulations for hard surfaces, and particularly dishwashing detergents.
• Particularly preferred mixtures within the meaning of the present technical teaching relate to combinations of the compounds of the formulas (Ia) and / or (Ib) with compounds of the formula (III).
• Fatty alcohols are primary aliphatic alcohols of the formula R-OH in which R is an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
• R is an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
• Typical examples are caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidy
• the compounds of the type a) and b) are preferably present in a weight ratio of 10: 1 to 1:10 side by side in the mixtures according to the invention. However, preference may be given to those mixtures in which the surface-active compounds of the type a) and b) in a weight ratio of 5: 1 to 1: 5, in particular from 3: 1 to 1: 3 and particularly preferably from 2: 1 to 1: 2 and most preferably 1: 1 are present side by side.
• the compounds of type b1) and / or b2) can - as stated above - also be present side by side in any mixtures. Preferably, however, the mixtures consist only of a compound of type a) and a compound of type b).
• the mixtures described above are preferably suitable for use in cleaners, in particular in dishwashing detergents and in particular in automatic dishwashing detergents.
• the mixtures can be used to improve the drying performance of cleaning agents and in particular for dishwashing detergents, preferably dishwasher detergents for automatic dishwashing.
• Another preferred use relates to the use of the mixtures in multifunctional solid Dishwashing detergents for automatic dishwashing. The improvement of the drying concerns in particular surfaces of plastic.
• agents which contain from 0.1 to 15% by weight of the mixtures according to the invention and also other ingredients customary in detergents and, preferably, dishwashing detergents.
• the detergents contain the mixtures according to the invention in amounts of from 0.1 to 12% by weight, advantageously from 1 to 10% by weight and in particular from 1.0 to 8% by weight. Particularly preferred is the range of 2.0 to 8.0 wt .-%.
• compositions according to the invention in the sense of the above description can be, for example, further nonionic, anionic and / or cationic surfactants, builders, enzymes, bleaching agents, such as e.g. Be percarbonates.
• agents may contain silicates, phosphorus compounds, carbonates, but also special rinse aids and other known and customary auxiliaries and additives, e.g. pH regulators or enzymes.
• solvents such as water or lower aliphatic alcohols, preferably ethanol or propanol, solubilizers, polymers or organic acids, preferably citric acid and derivatives thereof.
• the cleaning agents can be both liquid and solid, for example as granules, powders or tablets.
• Liquid detergents may still contain viscosity builders, e.g. to obtain gel-like agents.
• machine dishwashing detergents are in solid form, for example as powders or granules or as shaped articles, preferably in tablet form. There may also be several phases next to one another, for example a compressed tablet which contains in a bulge a non-compressed part, eg a waxy rinse aid phase.
• Such multifunctional agents are marketed as 2-in-1 or 3-in-1 products.
• the preparation is carried out in any manner known to the person skilled in the art, wherein in a preferred embodiment the mixtures according to the invention are present as a compound and are preferably mixed with the other ingredients in any order. But it is also possible to mix the surfactants of the type a) and b) individually with the other ingredients and, for example, then to press or granulate this mixture to the finished agent.
• Another object of the present application relates to the use of compounds of the general formulas (Ia) or (Ib) without the above-mentioned HME in detergents, preferably dishwashing detergents and particularly preferably in dishwashing detergents for automatic dishwashing.
• the compounds according to the formulas (Ia) or (Ib) can also develop advantageous effect in a cleaning agent without the use of the above-described HME, in particular with regard to an improved drying behavior of the rinsed objects, and preferably those articles which have plastic surfaces or Plastics exist.
• inventive 1 1 mixtures A to C were incorporated (at 8% by weight, based on the dishwashing detergent) in a commercial formulation for a solid automatic dishwashing agent.
• the assessment of the drying performance is done by counting the still adhering to the items to be washed after the rinsing process drops. Glasses, cutlery, plastic and porcelain plates are rinsed under defined conditions (water at 21 ° dH, 50 g standard soiling) in a household dishwashing machine. After completion of the wash program, the items to be washed are assessed under defined light conditions according to the number of drops.
• the results were made by comparing the drops of water remaining on a plastic surface after passing through the rinsing process.
• the standard formulation is composed of 2% by weight of a C8 / C10-alkyl-10E-22EO-hydroxy-C10-alkyl ether, 1% by weight. a polymer, 7% by weight of sodium silicate, 52% by weight of sodium triphosphate, 2.5% by weight of TAED, 27.5% by weight of sodium carbonate and 8% by weight of sodium percarbonate.
• the compositions containing mixtures A to C showed a reduction in the number of drops of plastic by 1 to 3.

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• 2008
  • 2008-02-14 DE DE102008009366A patent/DE102008009366A1/de not_active Withdrawn
• 2009
  • 2009-02-06 EP EP09711301A patent/EP2240562B1/fr active Active
  • 2009-02-06 CA CA2713335A patent/CA2713335A1/fr not_active Abandoned
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