EP2240562A2

EP2240562A2 - Use of surface-active substances in cleaning agents

Info

Publication number: EP2240562A2
Application number: EP09711301A
Authority: EP
Inventors: Teresa Alexandre; Hans-Christian Raths; Manfred Weuthen; Sabine Both
Original assignee: Cognis IP Management GmbH
Current assignee: Cognis IP Management GmbH
Priority date: 2008-02-14
Filing date: 2009-02-06
Publication date: 2010-10-20
Anticipated expiration: 2029-02-06
Also published as: EP2267110A2; EP2267110B1; EP2240562B1; CA2713335A1; ES2400791T3; PL2240562T3; US8148313B2; WO2009100855A3; CN101945986B; EP2267110A3; WO2009100855A2; ES2373084T3; DE102008009366A1; ATE523582T1; US20100323948A1; AU2009214382A1; CN101945986A

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

Use of surface-active substances in cleaning agents

The present invention relates to the use of selected surface-active substances, alone or in combination, for use in detergents 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 is especially true for automatic dishwashing. The three components of the mechanical system are cleaners, rinse aids and regeneration salts 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 determines the amount of i5 deposits on the dishes after they have been 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. To reduce the proportion of these deposits contain common dishwashing detergents, especially those for automatic

20 dishwashing, usually so-called rinse aid. Commercially available rinse aids are usually 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) in it, the interfacial tension of the water so too

25 influence that it can run off in a very thin, coherent film from the dishes, so that no drops of water, streaks or films remain during the subsequent drying process. There are differences between two types of deposits. On the one hand, the so-called "spotting" is investigated, which is created by drying water droplets, on the other hand, you evaluate the "filming", which are

3o layers, which result from the drying of thin water films. 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, they do not dry on all 5 substrates, like plastic as well. To get around this effect, consuming formulated conventional rinse aid, which have, for example, silicone compounds or fluorinated compounds, as described in US 5,880,089 or US 2005/0143280 Al. However, these compounds are biologically difficult or even not degradable and sometimes even dangerous to the environment.

5

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 lo. For example, so-called 3-in-1 products, which combine cleaners, rinse aids and water softening in the form of a solid tablet ("tabs"), are found in the market, however, as a result of the increased use of such multifunctional agents, the drying performance is higher than that of a The term "drying performance" is understood to mean the extent to which the washed ware still has water, preferably water droplets, on the surface after having passed through the dishwashing process.The water remaining on the surface must then either be removed mechanically (eg by drying) wipe) or allow the items to be air dried, so the user must wait for the water to evaporate, leaving residues on the surface (eg limescale and / or residues of surfactants or others)

2o residues that were dissolved or dispersed in the water) which lead to unaesthetic spots or streaks. This is especially true with glossy or transparent surfaces, e.g. Glass or metal. It is therefore sought ways to improve the drying performance of cleaning agents for hard surfaces, especially dishwashing detergents. EP 1 306 423 A2 discloses aqueous

25 detergents which contain alkyl ether sulfates and amphoteric glycine compounds and are suitable for improving the drying behavior of dishwashing detergents. DE 100 45 289 A1 describes hand dishwashing detergents which contain certain quaternary ammonium compounds and alkyl ether sulfates next to one another and likewise show particularly good drying behavior.

Furthermore, additives for cleaning agents must not adversely affect the rinsing and, in particular, the rinsing performance of the cleaners. 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.

The present invention therefore relates, in a first embodiment, to mixtures comprising at least two different surface-active substances from groups a) and b), the surface-active compound a) being selected from compounds which have the general formula (Ia):

0- (CH ₂ -CH ₂ -O) _n -CH ₂ -CH (OH) -R 'MI (Ia) O- (CH ₂ -CH ₂ -O) _m -CH ₂ -CH (OH) -R "

wherein M is a radical CH ₂ -CH ₂ or CHR-CH ₂ , R, R 'and R "independently represent 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) follow

0- (CH ₂ -CH ₂ -O) _n -R '"X'CX" (Ib) I

0- (CH ₂ -CH ₂ -O) ₀₁ -R ""

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 are H or are saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 1 to 18 C atoms and the component b) is selected from

bl) compounds of the general formula (II)

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OM) R ² (II) in which 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 is a number from 20 to 80, preferably 40 to 80, and M is a hydrogen atom or a saturated alkyl radical having 1 to 18 carbon atoms, and / or compounds of group b2) according to the general formula III

R ³ O [CH ₂ CH ₂ OIy [CH ₂ CHCH ₃ O] ₂ CH ₂ CH (OH) R ⁴ (III)

in which R ^{3 is} a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R ^{4 is} a linear or branched alkyl and / or alkenyl radical having 8 to 16 carbon atoms, y is a number of 10 and 35, z is zero or a number from 1 to 5, with the proviso that if R ³ = R ¹ and at the same time R ⁴ = R ² , then z must be at least 1.

EP 1 645 618 A1 of the Applicant already discloses mixtures of hydroxy mixed ethers according to the formulas (II) and (III) with polyol hydroxyalkyl ethers and their use in dishwashing detergents. However, these mixtures relate to the present application different components of the type a). The mixtures described contain at least one component selected from compounds of the formulas (Ia) or (Ib), and at least one compound selected from compounds of the formulas (II) or (III). The compounds of the formulas (Ia), (Ib), (II) and (III) are chemical compounds known to the person skilled in the art.

Compounds of group a)

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. In particular, 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.

s Also preferred are structures which follow the general formula (Ib):

0- (CH ₂ -CH ₂ -O) _n -R '"X'CX" (Ib)

IO I

O- (CH ₂ -CH ₂ -O) _m -R ""

where X 'and X "= H, and in the formula (Ib) the indices n and m can independently of one another assume values of 1 to 40, but preferably of 1 to 15. Particular preference is given here to compounds of the formula (Ib) 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 assume values from 1 to 15 and in particular from 1 to 12. Preference is furthermore given to those compounds of the formula (Ib) in which a radical R '' 'or R' '' is branched, independently of which compounds of the formula (Ib)

2o preferred in which the indices n and m are equal and have values in the range of 8 to 12.

The second component of the mixtures are compounds of the formulas (II) and (III), which can be referred to as hydroxy mixed ethers.

25

hydroxy mixed

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

RO [AO] _X CH ₂ CH (0M) 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, propylene oxide and / or butylene oxide radical and M can represent a hydrogen atom or an alkyl-5 or alkenyl radical. Such hydroxy mixed ethers are known from the literature and are described, for example, in German application DE 19738866. They are prepared, for example, by reaction of 1,2-epoxyalkanes (R ⁵⁵ CHOCH ₂ ), where R ^{55 is} an alkyl and / or alkenyl radical having 2 to 22, in particular 6 to 16, carbon atoms, with alkoxylated alcohols.

Preferred in the context 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 , 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.

Surface-active compounds of type b \)

These are commercially available surfactants of the general formula (II)

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OM) R ² (II)

in which 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. Advantageously, those compounds of the type b) of the general formula (II) are used which contain at least one free hydroxyl group (= -OH). 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. Furthermore, in the mixtures according to the invention 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. Very particular preference is given to hydroxy mixed ethers of the formula (II) where R ^{1 is} an alkyl radical having 8 to 10 carbon atoms, in particular based on a native fatty alcohol, R ^{2 is} an alkyl radical having 10 carbon atoms, in particular a linear alkyl radical and x is 40 to 60 stands. Preference is furthermore given to mixtures which contain as surface-active compound of type a) a compound of the general formula (II) in which R ^{1 is} an alkyl and / or alkenyl radical having 8 to 10 carbon atoms and R ^{2 is} an alkyl or Alkenyl radical having 8 to 10 carbon atoms and x is a number from 40 to 50, wherein also here M stands for a hydrogen atom.

A particularly preferred HME in the context of the present teaching follows the general formula

OH

I

R is -O- (CH ₂ CH ₂ O) _x -CH ₂ -CH-R ^"

Wherein R is a saturated alkyl radical having 8 to 12, preferably 8 to 10 carbon atoms and R represents an alkyl radical having 8 to 12, preferably 8 to 10 carbon atoms. The index x can have values from 20 to 80, preferably from 30 to 60 and in particular from 40 to 50, with those compounds in which the index x is greater than 40 generally being preferred.

Surface-active compounds of type b2)

These compounds are also HME, but they have a different structure than the HME of the general formula (II).

The compounds of the type b2) follow the formula (III)

R ³ O [CH ₂ CHCH ₃ O] ₂ [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ⁴ (III) in which R ^{3 is} a linear or branched alkyl and / or alkenyl radical having 8 to 22 carbon atoms, R ^{4 is} a linear or branched alkyl and / or alkenyl radical having 8 to 16 carbon atoms, y is a number of 10 and 35, z is zero or must be a number from 1 to 5. It may be advantageous if R ³ = R ¹ and at the same time R ⁴ = R ² those compounds of the formula b ² ) are selected in which the index z is at least 1. If mixtures of the surface-active compounds of the type a) with those of the type b2) are used, only those mixtures within the meaning of the present technical teaching in which the molecules structurally differ from one another. So there must always be different structure connections side by side.

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. Preference is furthermore given to those compounds of the type b2) in which 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 and 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.

Also preferred are 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 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. It is in the case of derivatives of the type b2) as well as in all other mixed alkoxylates listed in this description, that is to say 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. Furthermore, 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.

As far as the number of EO or PO groups in a molecule according to the formula of the present application is concerned, 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.

A particularly preferred type of HME of the general formula (III) is described by the following Markush formula:

OH

R is -O- (CH ₂ CH (CH ₃ ) O) _x -C CH ₂ CH ₂ O) _y CH ₂ -CH-R ^"

where R and R "independently of one another represent a saturated alkyl radical having 8 to 12, preferably 8 to 10 C atoms The index x can have values of 1 to 10, preferably 1 to 4 and in particular 1 to 2, and y has values of from 10 to 30, preferably from 15 to 25 and in particular from 20 to 22, whereby in general those compounds are preferred in which the index x = 1.

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). In addition to the surface-active compounds described above, it may be advantageous to use further surface-active compounds (ie surfactants). Pure fatty alcohols in particular come into question here.

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. 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 brassidyl alcohol and the like technical mixtures, eg incurred in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Preferred are technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol.

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 the type b1) and / or b2) can-as stated above-also be present side by side in any desired 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.

In a further embodiment, agents are claimed which contain from 0.1 to 15% by weight of the mixtures according to the invention, as well as other ingredients customary 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 .-%.

10

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 excipients 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 may 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, automatic dishwashing detergents are in solid form, e.g. as a powder or granules or as a shaped body, preferably in tablet form. There may also be several phases next to each other, for example a compressed tablet which has in a bulge a non-compressed part, e.g. contains 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 and 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. However, it is also possible to mix the surfactants of type a) and b) individually with the other ingredients and, for example, these

To blend or granulate the mixture to the finished product. 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.

Examples

Preparation of surface-active compounds

In addition, methods for producing the surface-active according to the invention

Compounds according to the general formulas (Ia) or (Ib) described:

1. Preparation of an ether according to formula (Ia):

Precursor ethoxylate: 1 mol of 1,2-dodecanediol and 0.06 mol of KOH as a 45% solution are placed under nitrogen in a stirred autoclave. 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 ⁰ C, the addition of 40 moles of ethylene oxide begins at a maximum pressure of 5bar. After the reaction is cooled to 120 ° C and evacuated for 30 min. For subsequent storage, the product is neutralized after cooling (preferably with lactic acid or acetic acid). For further implementation is not neutralized. The precursor is added under nitrogen with a further 0.05 mol of KOH and heated to 160-180 ° C. Then added dropwise 2 mol of 1, 2-epoxyhexadecane within 1 hour and stirred for 2 hours at 180 ° C after. Then it is also cooled to 60 ° C and neutralized (preferably with lactic acid or acetic acid).

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 12O ⁰ 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-butylglycol formal in the presence of an acidic catalyst, preferably methanesulfonic acid. For this purpose, fatty alcohol ethoxylate and di- 1.1 mol: 1.7 mol and initially with 6 g of methanesulfonic acid slowly raised 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 ⁰ C and 5 neutralized by addition of NaOH.

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

IMoI 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 lo bottom temperature and 5mbar butyl glycol and residues of the formal are distilled off.

It is then neutralized with NaOH or another base.

Application engineering investigations

Three mixtures (1: 1 w / w) of compounds according to the general formulas i5 (Ia) and (Ib) with a propoxylated hydroxy mixed ether according to the general formula (III) were prepared. As surfactants of group a) were used: C10-alkyldiol-40 EO di-2-hydroxyhexadecyl ether for the mixture A; Butylglycol-isotridecyl alcohol-9EO formal for mixture B; Di-C8 / C10-alkyl-1 EO formally for the mixture C. As hydroxymix ether of type b2), in each case a C8 / C10-alkyl-1E-22EO-hydroxy-C10-

20 alkyl ethers used.

These 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 25 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.

30

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. % of 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. Compared to the standard, the compositions containing mixtures A to C showed a reduction in the number of drops of plastic by 1 to 3.

Claims

claims

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

0- (CH ₂ -CH ₂ -O) _n -CH ₂ -CH (OH) -R '

M (Ia)

0- (CH ₂ -CH ₂ -O) ₁₁₁ -CH ₂ -CH (OH) -R "

wherein M is a radical CH ₂ -CH ₂ or CHR-CH ₂ , R, R 'and R "independently represent saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 6 to 22 carbon atoms, and the indices n and m can independently of one another assume values between 1 and 40, and / or compounds of the general formula (Ib)

0- (CH ₂ -CH ₂ -O) _n -R '"

X'CX "(Ib)

0- (CH ₂ -CH ₂ -O) _1n -R ""

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 H or represent saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 1 to 18 C atoms

and the compounds of type b) of the general formula (II)

R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OM) R ² (II)

in which 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} 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 is s and / or the general formula (III)

R ³ O [CH ₂ CHCH ₃ O] ₂ [CH ₂ CH ₂ OI _y CH ₂ CH (OH) R ⁴ (III)

in the R for a linear or branched alkyl and / or alkenyl radical having 8 to 22 lo carbon atoms, R ^{4 is} a linear or branched alkyl and / or

Alkenyl radical having 8 to 16 carbon atoms, y is a number of 10 and 35, z is zero or must be a number from 1 to 5, follow.

2. Mixtures according to Claim 1, characterized in that they contain only one surface-active compound a) in combination with only one surface-active compound

Compound b) included.

3. Mixture according to claims 1 to 2, characterized in that in the formula (Ia) R, R 'and R "are each a linear, saturated alkyl radical, wherein R

20 is an alkyl radical having 8 to 16, R 'and R "independently of one another with an alkyl radical

Represent 10 to 16 C atoms and n and m independently of one another assume a value of 20 to 30.

4. Mixtures according to claims 1 to 3, characterized in that in the formula (Ib) the radicals R '"or R" "independently represent saturated alkyl radical 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) of the index x for a number from 40 to 70, preferably 40 to 60 and in particular from 40 to 50 means.

6. Mixture according to claims 1 to 5, characterized in that in the formula

(III) the subscript y stands for a number from 20 to 30, preferably from 20 to 25.

7. Mixture according to Claims 1 to 6, characterized in that 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 1: 1 next to each other.

8. Mixture according to claims 1 to 7, characterized in that it contains as compound of the type bl) a compound of the general formula (II), in which R ^{1 is} an alkyl and / or alkenyl radical having 8 to 10 carbon atoms and R ^{2 is} an alkyl or alkenyl radical having 8 to 10 carbon atoms and x is a number from 40 to 50.

9. Mixture according to claims 1 to 8, characterized in that it contains as a 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 11 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.

10. Mixture according to claims 1 to 9, characterized in that it contains as a 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 an integer from 1 to 3.

11. Use of mixtures according to claims 1 to 10 in detergents and cleaners, preferably in cleaners for hard surfaces and in particular in detergents for automatic dishwashing.

12. Use according to claim 11, characterized in that one uses the mixtures in amounts of 0.1 to 15 wt .-%, preferably from 1 to 10 wt .-% in the detergents.

13. Use of mixtures according to claims 1 to 10, or the compounds according to the general formulas (Ia) or (Ib) for improving the drying performance of detergents, preferably dishwashing detergents.

14. Use of compounds according to the general formula (Ia)

0- (CH ₂ -CH ₂ -O) _n -CH ₂ -CH (OH) -R '

M (Ia)

0- (CH ₂ -CH ₂ -O) ₁₁₁ -CH ₂ -CH (OH) -R "

wherein M is a radical CH ₂ -CH ₂ or CHR-CH ₂ , R, R 'and R "independently represent 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 in detergents, in particular in dishwashing detergents.

15. Use of compounds according to the general formula (Ib)

0- (CH ₂ -CH ₂ -O) _n -R '"

X 'CX' (Ib)

O- (CH ₂ -CH ₂ -O) _m -R ""

in which 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 can independently of one another assume values between 1 and 40 and X' and X "independently of one another are H or saturated, unsaturated, linear or branched alkyl or alkenyl radicals having 1 to 18 C atoms and are present in cleaners, in particular in dishwashing detergents.

16. Cleaning agents contain 0.1 to 15 wt .-% of mixtures according to claims 1 to 10, or the compounds according to the formulas (Ia) or (Ib) and other nonionic, anionic and / or cationic surfactants, and optionally builder , Enzymes, rinse aids and / or other auxiliaries and additives.