EP2267110B1 - Use of surface-active substances in cleaning agents - Google Patents

Abstract

Mixture (I) comprises at least two different surface active substances of group (a) and (b), where: (a) is an ether compound (Ia) and/or an acetal compound (Ib); and (b) is an ether compound (II) and/or (III). Mixture (I) comprises at least two different surface active substances (a) and (b), where: (a) is an ether compound of formula (R1a-CH(OH)-CH 2-(O-CH 2-CH 2) n-O-M-O-(CH 2-CH 2-O) m-CH 2-CH(OH)-R2a) (Ia), and/or acetal compound of formula (R3a-(O-CH 2-CH 2) n-O-X1aCX2a-O-(CH 2-CH 2-O) m-R4a) (Ib); and (b) is an ether compound of formula (R 1>-O-[CH 2-CH 2-O] xCH 2CH(OM)R 2>) (II) and/or (R 3>-O-[CH 2-CHCH 3-O] z[CH 2CH 2O] yCH 2CH(OH)R 4>) (III). M : CH 2-CH 2or CHR-CH 2; R, R1a, R2a : optionally saturated 6-22C alkyl and/or 6-22C alkenyl; m, n : 1-40; R3a, R4a : optionally saturated 4-22C alkyl and/or 4-22C alkenyl; X1a, X2a : H or optionally saturated 1-18C alkyl and/or 1-18C alkenyl; R 3>8-22C alkyl or 8-22C alkenyl; R 4>8-16C alkyl or 8-16C alkenyl; x : 20-80, preferably 40-50; y : 10-35, preferably 20-35; and z : 0-5, preferably 1-3. An independent claim is included for a cleaning agent comprising: 0.1-15 wt.% of (I); other non-ionic, anionic and/or cationic surfactant; optionally forming agent, enzyme, rinsing agent and/or further auxiliary agents; and additives.

Description

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. This applies in particular to automatic dishwashing. The three components of the machine system are cleaner, rinse aid and regeneration salt for water softening. Here, 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. In order to reduce the proportion of these deposits, common dishwashing agents, in particular those for automatic dishwashing, generally contain so-called rinse aid. Commercially available 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. For the evaluation, test persons are currently used who visually evaluate the parameters "spotting" and "filming" for cleaned objects, eg plates, glasses, knives, etc. Modern dishwashing detergents, therefore, contain rinse aid to improve the drainage of water from the surfaces of the dishes. There are rinse aids that do not dry on all substrates, such as plastic as well. To get around this effect, consuming formulated conventional rinse aid, for example, have silicone compounds or fluorinated compounds, as described in the US 5,880,089 or the US 2005/0143280 A1 to be discribed. However, these compounds are biologically difficult or even not degradable and sometimes even dangerous to the environment.

Out EP 1254948 A1 are known as gemini surfactants and their use in detergents and cleaners. These are symmetrical hydroxymix ethers with free OH functions. The EP 1321511 A2 describes mixtures of gemini surfactants and fatty alcohol alkoxylates for rinse aid. In the EP 1288281 A2 Gemini surfactants are disclosed in combination with polyethylene glycols. The WO 95/13260 discloses a process for the preparation of blends of low foaming nonionic acetal surfactants. The document discloses its broad use in washing and cleaning processes in industry, commercial enterprises and in the household. The WO 96/00253 discloses hydroxyl-terminated polyoxyalkylenes in combination with acetals or ketals. Mixtures are suitable for various fields of application, including the cleaning of hard surfaces, especially in the industrial segment.

More recently, 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. Such agents are referred to as multifunctional agents. For example, 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. However, residues (eg lime and / or surfactant residues or other residues dissolved or dispersed in the water) remain on the surface which lead to unaesthetic spots or streaks. This applies in particular to shiny or transparent surfaces, such as glass or metal. It is therefore sought ways to improve the drying performance of cleaning agents for hard surfaces, especially dishwashing detergents. 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.

It has now been found that the combination of certain surface-active substances is suitable for improving the drying performance of hard-surface cleaners, in particular dishwashing compositions, and more particularly in multifunctional compositions, while being ecologically harmless.

worin R'" und R"" unabhängig voneinander für gesättigte, ungesättigte, lineare oder verzweigte Alkyl- bzw. Alkenylreste mit 4 bis 22 C-Atomen stehen, und die Indices n und m unabhängig voneinander Werte zwischen 1 und 40 annehmen können, X' und X" stehen unabhängig voneinander für gesättigte, ungesättigte, lineare oder verzweigte Alkyl- bzw. Alkenylreste mit 1 bis 18 C-Atomen stehen in Reinigungsmitteln, insbesondere Geschirrspülmitteln.The present invention is the use of compound of the general formula (Ib)

wherein R '"and R"' independently of one another represent saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 4 to 22 C atoms, and the indices n and m independently of one another can assume values between 1 and 40, X ' and X "independently of one another represent saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 1 to 18 C atoms in cleaning agents, in particular dishwashing agents.

From the EP 1 645 618 A1 the applicant are already known mixtures of Hydroxymischethern with Polyolhydroxyalkylethern and their use in dishwashing detergents. However, these mixtures relate to different components than the present application. Compounds of the formulas (Ib) are chemical compounds known to the person skilled in the art.

Particular preference is given here to compounds of the formula (1b) in which the radicals R "'and R" "independently of one another represent saturated alkyl radicals having 4 to 14 C atoms, and the indices n and m independently of one another have values from 1 to 15 and in particular from 1 to 12. Further preferred are those compounds of the formula (Ib) in which a radical R "'or R" "is branched. Independently of this, preference is given to compounds of the formula (Ib) in which the indices n and m are equal in number and have values in the range from 8 to 12.

hydroxy mixed

Hydroxy mixed ethers (hereinafter abbreviated to HME) follow the broad general formula

R ^'O [AO] _x CH ₂ CH (OM) R ^"

in which R ^'is a linear or branched alkyl and / or alkenyl radical having 4 to 22 carbon atoms, R "is a linear or branched alkyl and / or alkenyl radical having 2 to 22 carbon atoms x is 10 to 80 and AO is an ethylene oxide radical , Propylene oxide and / or butylene oxide radical symbolized and M can stand for a hydrogen atom or an alkyl or alkenyl radical.

Such 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.

Preferred for the purposes of the invention are those hydroxy mixed ethers which are derived from alkoxylates of monohydric alcohols of the formula R'-OH having 4 to 18 carbon atoms, where R 'is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, stands. Examples of 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. Examples of branched alcohols are 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.

In a further embodiment, agents are claimed which contain 0.1 to 15 wt .-% of the mixtures according to the invention, as well as other ingredients commonly used in detergents and, preferably, dishwashing detergents. Preferably, 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 .-%.

The usual ingredients of the 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. Furthermore, such 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. In addition, 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.

Preferably, 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. Another object of the present application relates to the use of compounds of the general formulas (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 formula (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 articles, and preferably those articles which have plastic surfaces or consist of plastics.

Examples Preparation of surface-active compounds

In addition, processes for the preparation of the surface-active compounds according to the invention according to the general formulas (Ia) or (Ib) are described:

2. Preparation of an acetal according to (Ib);

Precursor fatty alcohol ethoxylate: 1 mol of decanol and 0.03 mol of KOH as a 45% solution are placed in a stirred autoclave under nitrogen. The mixture is then evacuated at 120 ° C for 30 min. The vacuum is then quenched with nitrogen and heated to 160-180 ° C. At 160 ° C, the addition of 9 moles of ethylene oxide begins at a maximum pressure of 5 bar. After the reaction is cooled to 120 ° C and evacuated for 30 min. For subsequent storage or reuse, the product is neutralized after cooling (preferably with lactic acid or acetic acid).

3. Preparation of an unsymmetrical acetal according to (Ib):

The fatty alcohol ethoxylate prepared in accordance with 1. is reacted with excess di-butyl glycol formal in the presence of an acidic catalyst, preferably methanesulfonic acid. For this purpose, fatty alcohol ethoxylate and di-butylglykolformal in a molar ratio of about 1.1 mol: submitted to 1.7 mol and slowly raised with 6g of methanesulfonic acid to 180 ° C at a pressure of about 5 mbar. At a Brüdentemperatur of about 121-137 ° C distilled butyl glycol and excess formal. The product is then cooled to 50-70 ° C and neutralized by addition of NaOH.

4. Preparation of a symmetrical acetal according to (Ib):

1 mole fatty alcohol ethoxylate acc. 3) and 0.5 mol of di-butylglykolformal are placed under nitrogen and treated with 0.02 mol of sulfuric acid. At 97-152 ° C bottom temperature and 5mbar butyl glycol and residues of the formal are distilled off. It is then neutralized with NaOH or another base.

Claims (14)

1. Mixtures comprising at least two different surface-active substances from the groups a) and b), where the surface-active compound a) is selected from compounds of the general formula (Ia)

   

   in which M is a radical CH₂-CH₂ or CHR-CH₂, R, R' and R", independently of one another, are saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 6 to 22 carbon atoms, and the indices n and m, independently of one another, can assume values between 1 and 40, and/or compounds of the general formula (Ib)

   

   in which R"' and R"", independently of one another, are saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 4 to 22 carbon atoms, and the indices n and m, independently of one another, can assume values between 1 and 40, X' and X", independently of one another, are H or saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 1 to 18 carbon atoms
   and the compounds of type b) correspond to the general formula (II)
   
           R¹O[CH₂CH₂O]_xCH₂CH(OM)R²     (II)
   
   in which R¹ is a linear or branched alkyl and/or alkenyl radical having 4 to 22 carbon atoms, or is a radical R²-CH (OH) CH₂, where R² is a linear or branched alkyl and/or alkenyl radical having 8 to 16 carbon atoms, x is a number from 20 to 80, preferably from 40 to 80, and M is a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms
   and/or the general formula (III)
   
           R³O[CH₂CHCH₃O]_z[CH₂CH₂O]_yCH₂CH (OH) R⁴     (III)
   
   in which R³ is a linear or branched alkyl and/or alkenyl radical having 8 to 22 carbon atoms, R⁴ is a linear or branched alkyl and/or alkenyl radical having 8 to 16 carbon atoms, y is a number from 10 to 35, z is zero or must be a number from 1 to 5.
2. Mixtures according to Claim 1, characterized in that it comprise only one surface-active compound a) in combination with only one surface-active compound b).
3. Mixtures according to Claims 1 to 2, characterized in that, in the formula (Ia), R, R' and R" are in each case a linear, saturated alkyl radical, where R is an alkyl radical having 8 to 16 carbon atoms, R' and R", independently of one another, are an alkyl radical having 10 to 16 carbon atoms and n and m, independently of one another, assume a value from 20 to 30.
4. Mixtures according to Claims 1 to 3, characterized in that, in the formula (Ib), the radicals R"' and R"", independently of one another, are saturated alkyl radicals having 4 to 14 carbon atoms, and the indices n and m, independently of one another, assume values from 1 to 15 and in particular from 1 to 12.
5. Mixtures according to Claims 1 to 4, characterized in that, in the formula (II), the index x is a number from 40 to 70, preferably 40 to 60 and in particular from 40 to 50.
6. Mixtures according to Claims 1 to 5, characterized in that, in the formula (III), the index y is a number from 20 to 30, preferably from 20 to 25.
7. Mixtures according to Claims 1 to 6, characterized in that the surface-active compounds of type a) and b) are present alongside one another in the weight ratio of from 5 : 1 to 1 : 5, in particular of from 3 : 1 to 1 : 3 and particularly preferably of 1 : 1.
8. Mixtures according to Claims 1 to 7, characterized in that it comprises, as surface-active compound of type b1), a compound according to the general formula (II) in which R¹ is an alkyl and/or alkenyl radical having 8 to 10 carbon atoms and R² is an alkyl or alkenyl radical having 8 to 10 carbon atoms and x is a number from 40 to 50.
9. Mixtures according to Claims 1 to 8, characterized in that it comprises, as surface-active compound of type b2), a compound according to the general formula (III) in which R³ is an alkyl and/or alkenyl radical having 11 to 18 carbon atoms and R⁴ is an alkyl or alkenyl radical having 8 to 10 carbon atoms and y is a number from 20 to 35.
10. Mixtures according to Claims 1 to 9, characterized in that it comprises, as surface-active compound of type b2), a compound according to the general formula (III) in which R³ is an alkyl and/or alkenyl radical having 8 to 12 carbon atoms and R⁴ 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.
11. Use of mixtures according to Claims 1 to 10 in washing and cleaning agents, preferably in cleaning agents for hard surfaces and in particular in cleaning agents for automatic dishwashing.
12. Use according to Claim 11, characterized in that the mixtures are used in the cleaning agents in amounts of from 0.1 to 15% by weight, preferably from 1 to 10% by weight.
13. Use of mixtures according to Claims 1 to 10, for improving the drying performance of cleaning agents, preferably of dishwashing agents.
14. Cleaning agent comprising 0.1 to 15% by weight of mixtures according to Claims 1 to 10, and further nonionic, anionic and/or cationic surfactants, and also optionally builders, enzymes, rinse aids and/or further auxiliaries and additives.