DE10218752A1 - Alkoxylate mixture used in laundry and cleaning detergents for washing and cleaning textiles contains alkoxylates of alkanols with different chain lengths with ethylene oxide and optionally other alkylene oxide(s) - Google Patents

Abstract

Alkoxylate mixture contains 0.1-99.9 wt.% alkoxylate(s) (I) of 8-11 carbon (C) alkanol(s) and 0.1-99.9 wt.% alkoxylate(s) (II) of 12-24 C alkanol(s), in which (I) has 1-20 and (II) has 1-50 ethylenoxy groups, (I) and (II) have 0-10, optionally mixed 3-10 C alkylenoxy groups and the ethylenoxy and other alkylenoxy groups have random or alternating distribution or are in 2 or more blocks in any sequence. Alkoxylate mixture contains 0.1-99.9 wt.% alkoxylate(s) (I) and 0.1-99.9 wt.% alkoxylate(s) (II) of the given formulae, in which the ethylenoxy and other alkylenoxy groups have random or alternating distribution or are in 2 or more blocks in any sequence: R1 = CnH2n+1; R2 = CmH2m+1; A = ethylenoxy; B = 3-10 C alkylenoxy or a mixture of such groups; n = 8-11; m = 12-24; x = 1-20; = 1-50; y, w = 0-10 . An Independent claim is also included for production of the alkoxylate mixture by reacting the corresponding alkanols with 2-5 C alkylene oxides under alkoxylation conditions, using a double metal cyanide compound as catalyst, and mixing them before or after alkoxylation or after partial alkoxylation.

Description

The invention relates to alkoxylate mixtures and detergents containing them as well Process for the preparation of the alkoxylate mixtures and the use of the detergent for washing or cleaning textiles.

Detergents in the sense of this invention are usually used to wash more or less flexible materials, preferably those that are natural, synthetic or contain or consist of semisynthetic fiber materials and consequently at least partially have a textile character.

Detergents of this type have been described many times in the prior art. A very good overview of the mode of action and the composition of detergents can be found, for example, in Ullmanns Encyclopedia of Industrial Chemistry, 5th edition, Vol. A8, (1986), pages 315 ff, keyword "Detergents" and in Tai, Formulating Detergents and Personal Care Products, AOCS Press, 2000. The detergents contain one or more surfactants from the same or different surfactant groups and, as a rule, further auxiliaries and additives which are either required for packaging and / or which adapt the detergents to the specific intended use or the type of application (hand or machine wash). Components that can be used in many detergents in addition to the various surfactants in changing combinations and proportions are, for example, builders (sequestering agents) and co-builders, pH regulators, such as inorganic or organic acids, inorganic or organic bases and buffer systems, ion exchangers, Dispersants, dirt-carrying agents, thickeners, enzymes, bleaching systems, hydrotropic compounds as solubilizers or solubilizers, such as. B. urea or alcohols, foam regulators to stabilize or dampen the foam, skin and corrosion inhibitor, disinfectant compounds or systems, for example those containing iodine or which release chlorine or hypochlorous acid, such as. B. dichloroisocyanurate, perfume, dyes, optical (fluorescent) brighteners, graying inhibitors, adjusting and confectioning agents and disinfectant compounds. The surfactants contained therein have a significant share in the cleaning action of the detergents described in the prior art. Ionic surfactants are used, namely both anionic such as alcohol sulfates, alcohol ether sulfates, alkylbenzenesulfonates, α-olefin sulfonates, sulfosuccinates and cationic surfactants, such as. B. C ₈ to C ₁₆ dialkyldimethylammonium salts, dialkoxydimethylammonium salts or imidazolinium salts with long-chain alkyl radical.

The use of amphoteric surfactants, for example derivatives of secondary or tertiary amines such as. B. C ₆ -C ₁₈ alkyl betaines or C ₆ -C ₁₅ alkyl sulfobetaines or amine oxides such as alkyldimethylamine oxides have already been described.

Also nonionic surfactants, in particular also alkoxylates and polyglycosides from Alkanols with in particular 8 to 20 carbon atoms and alkoxylates of alkylamines and Alkyl amides are used in detergents. In particular, it is also known Alkoxylates of oxo alcohols with 10 to 13 carbon atoms as surfactants in detergents use. Such alkoxylates are described in DE-A-100 29 692.

In the interest of the most economical use of materials, high economy and The detergent manufacturers strive for a constant low environmental impact Improve the effectiveness of your products and especially the ones they contain Surfactants.

The object of the present invention is to provide alcohol alkoxylate Surfactant systems that improve in detergents and cleaning agents Dirt removal and the range of services of detergents and cleaning agents improve.

The object is achieved by a
Alkoxylate mixture containing
0.1 to 99.9% by weight of at least one alkoxylate of the general formula (I)

C _n H _{2n + 1} O (A) _x (B) _y H (I)

with the meaning
A ethyleneoxy
BC ₃ -C ₁₀ alkyleneoxy, preferably propyleneoxy, butyleneoxy, pentyleneoxy or mixtures thereof,
groups A and B can be statistically distributed, alternating or in the form of two or more blocks in any order,
n integer in the range from 8 to 11,
x number in the range from 1 to 20,
y number in the range from 0 to 10, and
0.1 to 99.9% by weight of at least one alkoxylate of the general formula (II)

C _m H _{2m + 1} O (A) _v (B) _w H (II)

with the meaning
A ethyleneoxy
BC ₃ -C ₁₀ alkyleneoxy, preferably propyleneoxy, butyleneoxy, pentyleneoxy or mixtures thereof,
groups A and B can be statistically distributed, alternating or in the form of two or more blocks in any order,
m integer in the range from 12 to 24,
v number in the range from 1 to 50,
w Number in the range from 0 to 10.

It has been found according to the invention that the alkoxylate mixtures, which differ from derive shorter-chain and longer-chain alkanols, a compared to known systems show significantly improved washing behavior. The improvement is particularly in the Comparison clearly compared to the use of only short-chain alkanol ethoxylates. The Use of such short-chain alkanol alkoxylates in detergent compositions is known per se.

WO 94/11331 relates to the use of alkoxylates of 2-propylheptanol in Detergent compositions for degreasing hard surfaces. The alkoxylates have 2 up to 16 alkylene oxide groups. Preferably the majority of the Alkylene oxide groups in the form of ethylene oxide. According to the examples only ethoxylated alcohols are used. It is also described that the Alcohols are first reacted with ethylene oxide and then with propylene oxide can. However, there are no examples or properties of such alkoxylates specified. It is stated that the alkoxylates described have good detergent properties. and show wetting effect combined with low foaming. In addition, indicated that the alkoxylates have a desired thickening effect in formulations to have.

WO 94/11330 relates to alkoxylates of 2-propylheptanol and their use. In the Alkoxylates is 2-propylheptanol, first with 1 to 6 mol of propylene oxide and then with 1 to 10 mol of ethylene oxide reacted before. According to the examples, a 4 mol Propylene oxide and then 2-propylheptanol reacted with 6 mol ethylene oxide used. The alkylene oxide adducts are said to have an improved ratio from foaming behavior to detergent effect. It is also stated that the Alkoxylates show good wetting behavior. You will be in Detergent compositions used for cleaning textile materials.

In US 2,508,036 are ethoxylates of 2-n-propylheptanol with 5 to 15 moles of ethylene oxide described. It is stated that the alkoxylates have improved wetting behavior show in aqueous solutions and therefore in detergents in combination with builders can be used.

In the following, the short-chain and long-chain alkanol alkoxylate components of the Alkoxylate mixtures according to the invention explained in more detail.

The mixtures according to the invention contain 0.1 to 99% by weight, preferably 10 to 90% by weight, in particular 20 to 70 wt .-% of at least one alkoxylate of the general Formula (I). Correspondingly, they contain 0.1 to 99% by weight, preferably 10 to 90% by weight, in particular 30 to 80 wt .-% of at least one alkoxylate of the general Formula (II).

In the alkoxylate of the general formula (I), A has the meaning ethyleneoxy. B means preferably propyleneoxy, butyleneoxy, pentyleneoxy or mixtures thereof, preferably Propyleneoxy or butyleneoxy, especially propyleneoxy.

n is an integer in the range from 8 to 11, preferably n has the value 10. It can be linear or branched alkyl radicals, and mixtures of linear and branched alkyl radicals can also be present. In the alkoxylate of the general formula (I), in which n has the value 10, the radical C ₁₀ H _{21 is} particularly preferably C ₅ H ₁₁ CH (C ₃ C ₇ ) CH ₂ . The shorter-chain alkoxylate is thus preferably derived from 2-propylheptanol, and mixtures of isomers may also be present.

For example, in the alkoxylate of the general formula (I)
70 to 99% by weight, preferably 85 to 96% by weight
Alkoxylates A1 in which C ₅ H _{11 has} the meaning nC ₅ H ₁₁ , and
1 to 30% by weight, preferably 4 to 15% by weight
Alkoxylates A2 in which C ₅ H _{11 has} the meaning C ₂ H ₅ CH (CH ₃ ) CH ₂ and / or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ ,
are present in the mixture. C ₃ H ₇ preferably has the meaning nC ₃ H ₇ .

The production of 2-propylheptanol (s) can start from valeraldehyde Aldol condensation and subsequent hydrogenation take place. The production of Valeraldehyde and the corresponding isomers are obtained by hydroformylation of Butene, such as in US 4,287,370; Beilstein E IV 1, 3268, Ullmanns Encyclopedia of Industrial Chemistry, 5th edition, volume A1, pages 323 and 328f described. The following aldol condensation is described for example in US 5,434,313. The hydrogenation of the aldol condensation product generally follows Hydrogenation conditions.

Furthermore, 2-propylheptanol can be condensed by 1-pentanol (as a mixture the corresponding methylbutanols-1) in the presence of KOH at elevated temperatures are produced, see e.g. B. Marcel Guerbet, C.R. Acad Sci Paris 128, 511, 1002 (1899). Furthermore, Römpp, Chemie Lexikon, 9th edition, Georg Thieme Verlag Stuttgart, and the quotes there as well as Tetrahedron 1967, vol. 23, pages 1723-1733.

In the general formula (I), x is a number in the range from 1 to 20, preferably 3 to 12. y is a number in the range from 0 to 10, preferably 0 to 5, particularly preferably y has the value 0. The values of x and y represent mean values, since in the alkoxylation of Alkanols usually get a distribution of the degree of alkoxylation. Therefore x and y, like the v and w discussed below, can be integer values differ. The degree of alkoxylation can be distributed to some extent Use of different alkoxylation catalysts can be set. Be next to Ethylene oxide also one or more longer chain alkylene oxides for alkoxylation used, the different alkylene oxide residues can be statistically distributed, alternating or in the form of two or more blocks in any order. It is particularly preferred to alkoxylate only with ethylene oxide, so that a pure (Poly) ethylene oxide residue is present. The mean of the homolog distribution is given by the indicated numbers x and y.

• - Oxoalkohole auf Basis von linearen oder verzweigten Olefinen,
• - sekundäre Alkohole, beispielsweise gewonnen durch Paraffinoxidation,
• - Alkohole, gewonnen durch den SHOP-Prozess,
• - Alkohole, erhältlich über die GTL-Technologie,
• - Alkohole, erhältlich über die Fischer-Tropsch-Technologie,
• - Alkohole, erhältlich über Gerüstisomerisierung der zur Oxierung eingesetzten Olefine entsprechend WO 98/23566.

In the longer-chain alkoxylate of the general formula (II), A and B preferably have the meaning given above. m is an integer in the range from 12 to 24, preferably from 12 to 18, particularly preferably from 12 to 15. The alkyl radical C _m H _{2m + 1} can be linear or branched. Mixtures of linear and branched alkyl radicals can also be present. They can come from any suitable source. The linear alcohols are of native or synthetic origin. Examples of branched alcohols include:

• Oxo alcohols based on linear or branched olefins,
• secondary alcohols, for example obtained by paraffin oxidation,
• - alcohols obtained through the SHOP process,
• - alcohols, available via GTL technology,
• - alcohols, obtainable via Fischer-Tropsch technology,
• - Alcohols, obtainable via framework isomerization of the olefins used for the oxidation in accordance with WO 98/23566.

v is a number in the range from 1 to 50, preferably from 3 to 15. b is a number in Range from 0 to 10, preferably in the range from 0 to 5. In particular, w has the value 0. It can refer to the above statements on x and y for the shorter chain Alcohol alkoxylates are referred.

The invention also relates to a process for the preparation of alkoxylate mixtures as described above, in which alkanols of the general formula C _n H _{2n + 1} OH and C _m H _{2m + 1} OH with the meaning given for n and m with C _2-5 Alkylene oxides are reacted under alkoxylation conditions and mixed with one another before or after the alkoxylation or after a partial alkoxylation.

The alkoxylation can be carried out, for example, using alkaline catalysts such as alkali metal hydroxides, alkali metal alcoholates. By using this Catalysts result in special properties, especially the distribution of the Alkoxylation.

The alkoxylation can also be carried out using Lewis acid catalysis with the resulting special properties, in particular in the presence of BF ₃ × H ₃ PO ₄ , BF ₃ dietherate, SbCl ₅ , SnCl ₄ × 2 H ₂ O, DMC, hydrotalcite ,

The excess alcohol can be distilled off or the alkoxylate can a two-step process can be won. Also the production of mixed alkoxylates from, for example, EO and PO is possible, with the alkanol radical initially Polyethylene oxide block and then an ethylene oxide block can connect, or first an ethylene oxide block and then a propylene oxide block. Also statistical / random distributions are possible. Preferred implementation conditions are given below.

The alkoxylation is preferably catalyzed by strong bases which are advantageously added in the form of an alkali metal hydroxide or alkaline earth metal hydroxide, generally in an amount of 0.1 to 1% by weight, based on the amount of the alkanol R ² -OH. (See G. Gee et al., J. Chem. Soc. (1961), p. 1345; B. Wojtech, Makromol. Chem. 66, (1966), p. 180)

Acid catalysis of the addition reaction is also possible. In addition to Bronsted acids, Lewis acids such as. B. AlCl ₃ or BF ₃ . (See PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press, New York (1963).

The addition reaction is preferred at temperatures from about 90 to about 240 ° C from 120 to 180 ° C, carried out in a closed vessel. The alkylene oxide or Mixture of different alkylene oxides is the mixture of the invention Alkanol mixture and alkali below that at the chosen reaction temperature prevailing vapor pressure of the alkylene oxide mixture supplied. If desired, can the alkylene oxide can be diluted up to about 30 to 60% with an inert gas. Thereby will provide additional security against explosive polyaddition of the alkylene oxide given.

If an alkylene oxide mixture is used, polyether chains are formed in which the various alkylene oxide building blocks are practically statistically distributed. Variations in the Distribution of the building blocks along the polyether chain result from different Reaction speeds of the components and can also be arbitrary continuous delivery of an alkylene oxide mixture programmatically Composition can be achieved. The different alkylene oxides are successively reacted so you get polyether chains, with block-like distribution of Alkylene oxide units.

The length of the polyether chains varies statistically within the reaction product an average value that essentially results from the additional quantity corresponds to the stoichiometric value.

The alkoxylate mixtures according to the invention are preferably in washing or Detergents used in which they improve the washing properties to lead. The invention also relates to a washing or cleaning agent containing a like alkoxylate mixture described above. The alkoxylate mixture becomes usually in an amount of 0.01 to 80 wt .-%, preferably in an amount of 0.01 to 50 wt .-%, based on the detergent or cleaning agent used. The Detergent or cleaning agent is preferably used for washing or cleaning Textiles used.

The minimum proportion of the alkoxylate mixtures according to the invention in the total weight of the Detergent according to the invention is dimensioned so that there is a significant effect of this addition shows. As a rule, a good washing effect, especially a very good one good primary washing action of the detergents according to the invention is achieved if the proportion of the mixtures in the detergent according to the invention, based on the total weight of the agent, 0.01 to 50% by weight, preferably 0.1 to 40% by weight, in particular 0.5 to 30% by weight is.

Detergents in the sense of this invention are usually used to wash more or less flexible. Materials, preferably those that are natural, synthetic or contain or consist of semisynthetic fiber materials and consequently in the Usually at least partially have a textile character. The fibrous or out Fibrous materials can, in principle, be used in any manufacturing or manufacturing and processing. For example, fibers can be disordered in the form of flakes or piles, arranged in the form of threads, yarns, threads, or in Form of fabrics such as nonwovens, loden fabrics or felt, woven fabrics, knitted fabrics in all conceivable types of binding exist.

It can be raw fibers or fibers in any processing stages and natural protein or cellulose fibers such as wool, silk, cotton, sisal, hemp, Coconut fibers or synthetic fibers such as polyester, polyamide or Be polyacrylonitrile fibers.

The detergents according to the invention can also be used to clean fiber-containing detergents Materials such as B. back-coated carpets with cut or uncut pile.

The compositions of the detergents are preferably used for various purposes adapted as is known to the person skilled in the art from the prior art. For this, the detergents according to the invention all appropriate from the prior art known auxiliaries and additives are added.

• - Builder und Cobuilder, wie Polyphosphate, Zeolithe, Polycarboxylate, Phosphonate oder Komplexbildner
• - ionische Tenside, wie Alkoholsulfate/-ethersulfate, Alkylbenzolsulfonate, α- Olefinsulfonate und andere Alkoholsulfate/-ethersulfate
• - andere nichtionische Tenside, wie Alkylaminalkoxylate, Alkylpolyglucoside
• - optische Aufheller
• - Farbübertragungsinhibitoren, wie Polyvinylpyrrolidon der Molmassen 8.000 bis 70.000, Vinylimidazol/Vinylpyrrolidon-Copolymere mit einem Molverhältnis der Monomeren von 1 : 10 bis 2 : 1 und Molmassen von 8.000 bis 70.000 sowie Poly-4-vinylpyridin-N-oxide mit Molmassen von 8.000 bis 70.000.
• - Stellmittel, wie Natriumsulfat oder Magnesiumsulfat
• - Soil Release-Mittel
• - Inkrustationsinhibitoren
• - Bleichsysteme, enthaltend Bleichmittel, wie Perborat, Percarbonat und Bleichakitvatoren, wie Tetraacetylethylendiamin sowie Bleichstabilisatoren
• - Parfum/-öle
• - Schaumdämpfer, wie Silikonöle
• - Enzyme, wie Amylasen, Lipasen, Cellulasen, Proteasen
• - Alkalispender, wie lösliche Alkalisilikate, z. B. Pentanatriummethasilikat, Nariumcarbonat.

In addition to the mixtures according to the invention, detergents may contain, for example:

• - Builders and cobuilders, such as polyphosphates, zeolites, polycarboxylates, phosphonates or complexing agents
• - Ionic surfactants such as alcohol sulfates / ether sulfates, alkylbenzenesulfonates, α-olefin sulfonates and other alcohol sulfates / ether sulfates
• - Other nonionic surfactants, such as alkylamine alkoxylates, alkyl polyglucosides
• - optical brighteners
• - Color transfer inhibitors, such as polyvinylpyrrolidone of molecular weights 8,000 to 70,000, vinylimidazole / vinylpyrrolidone copolymers with a molar ratio of the monomers of 1:10 to 2: 1 and molecular weights of 8,000 to 70,000, and poly-4-vinylpyridine-N-oxides with molecular weights of 8,000 to 70,000.
• - adjusting agents, such as sodium sulfate or magnesium sulfate
• - Soil release funds
• - incrustation inhibitors
• - Bleaching systems containing bleaching agents, such as perborate, percarbonate and bleach activators, such as tetraacetylethylene diamine and bleach stabilizers
• - perfume / oils
• - foam absorbers, such as silicone oils
• - Enzymes, such as amylases, lipases, cellulases, proteases
• - Alkaline dispensers, such as soluble alkali silicates, e.g. B. pentasodium methasilicate, sodium carbonate.

In liquid detergents, for example, solvents such as ethanol, Isopropanol, 1,2-propylene glycol, butyl glycol, etc. can be used.

In tablet detergents, tableting aids such as Polyethylene glycols with molar masses of more than 1000 g / mol, polymer dispersions as well Tablet disintegrants, such as cellulose derivatives, crosslinked polyvinylpyrrolidone, crosslinked Polyacrylates or combinations of acids such as citric acid and sodium bicarbonate be used. A more detailed listing of possible ingredients is given below given.

In some cases, it may be appropriate to use the mixtures used according to the invention with other nonionic surfactants, such as alkylamine alkoxylates, alkylamide alkoxylates, Alkyl polyglucosides, or with ionic, preferably anionic, surfactants, such as. B. Alcohol sulfate ether sulfates, alkylbenzenesulfonates, α-olefin sulfonates, sulfosuccinates, or with amphoteric surfactants, such as. B. alkylamine oxides, or betaines to combine.

The following are examples of different types of surfactants suitable for combination:
A class of suitable nonionic surfactants are alkylphenol alkoxylates such as alkylphenol ethoxylates with C ₆ to C ₁₄ alkyl chains and 5 to 30 moles of alkylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides with 6 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These connections usually contain 1 to 20, preferably 1.1 to 5, glucoside units.

Another class of nonionic surfactants are N-alkyl glucamides of the general structures


where B ^{1 is} a C ₆ to C ₂₂ alkyl, B ^{2 is} hydrogen or C ₁ to C ₄ alkyl and D is a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxy groups. B ¹ is preferably C ₁₀ to C ₁₈ alkyl, B ^{2 is} CH ₃ and D is a C ₅ or C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ to C ₁₈ carboxylic acids.

Other suitable nonionic surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A 95/11225

R ¹ -CO-NH- (CH ₂ ) _y -O- (A ¹ O) _x -R ²

in the
R ¹ denotes a C ₅ to C ₂₁ alkyl or alkenyl radical,
R ^{2 represents} a C ₁ to C ₄ alkyl group,
A ^{1 represents} C ₂ to C ₄ alkylene,
y denotes the number 2 or 3 and
x has a value from 1 to 6.

Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₃ -C ₄ H ₉ with methyl dodecanoate or the reaction products of ethyl tetraglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated C ₈ - to C ₁₈ -fatty acid methyl esters.

Also suitable as nonionic surfactants are block copolymers of ethylene oxide, Propylene oxide and / or butylene oxide (Pluronic® and Tetronic® brands from BASF), Polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N- Alkoxy- or N-aryloxypolyhydroxy fatty acid amides, fatty acid amide ethoxylates, in particular end group-capped and fatty acid alkanolamide alkoxylates.

The additional nonionic surfactants ("nonionic surfactants") are in the invention Detergents preferably in an amount of 0.01 to 30 wt .-%, in particular 0.1 to 25% by weight, especially 0.5 to 20% by weight.

It is also possible to use individual nonionic surfactants or a combination of different nonionic surfactants. Nonionic surfactants from only one class can be used, in particular only alkoxylated C ₈ to C ₂₂ alcohols, but surfactant mixtures from different classes can also be used.

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, C ₁₂ -C ₁₈ alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by firstly using a C ₈ - to C ₂₂ -, preferably a C ₁₀ - to C ₁₈ alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated. Ethylene oxide is preferably used for the alkoxylation, 1 to 50, preferably 1 to 20, mol of ethylene oxide being used per mol of alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Such alkoxylated C ₈ are suitable also - to C ₂₂ alcohols, the ethylene oxide and propylene oxide or ethylene oxide and butylene oxide or ethylene oxide and propylene oxide and butylene oxide. The alkoxylated C ₈ to C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution. Depending on the type of alkoxylation catalyst, alkyl ether sulfates with a broad or narrow alkylene oxide homolog distribution can be obtained.

Other suitable anionic surfactants are alkane sulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₁₈ alkane sulfonates and soaps such as the Na and K salts of saturated and / or unsaturated C ₅ to C ₂₄ carboxylic acids.

Other suitable anionic surfactants are linear C ₈ to C ₂₀ alkylbenzenesulfonates ("LAS"), preferably linear C ₉ to C ₁₃ alkylbenzenesulfonates and alkyltoluenesulfonates.

Also suitable as anionic surfactants are C ₈ to C ₂₄ olefin sulfonates and disulfonates, which can also be mixtures of alkene and hydroxyalkane sulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyate, paraffin glycolsulfonate with parolinesulfonate, paraffin 20 up to approx. 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl taurates, acyl methyl taurates, alkyl succinic acids, alkenyl succinic acids or their half esters or half amides, alkyl sulfosuccinic acids or their amides, mono- and diesters of sulfosuccinic acids, acyl sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

The anionic surfactants are preferably added to the detergent in the form of salts added. Suitable cations in these salts are alkali metal ions such as sodium, Potassium and lithium and ammonium salts such as B. hydroxyethylammonium, Di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

The anionic surfactants in the detergents according to the invention are preferably present in an amount of up to 30% by weight, for example 0.1 to 30% by weight, especially 1 to 25% by weight, in particular 3 to 20% by weight. % in front. If C ₉ to C ₂₀ linear alkylbenzenesulfonates (LAS) are also used, these are usually used in an amount of up to 15% by weight, in particular up to 10% by weight.

One can use individual anionic surfactants or a combination of different anionic surfactants deploy. Anionic surfactants from only one class can be used for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but you can also Use surfactant mixtures from different classes, e.g. B. a mixture of Fatty alcohol sulfates and alkylbenzenesulfonates.

Furthermore, the surfactant mixtures to be used according to the invention with cationic surfactants, usually in an amount of up to 25% by weight, preferably 1 to 15% by weight, for example C ₈ to C ₁₆ dialkyldimethylammonium salts, dialkoxydimethylammonium salts or imidazolinium salts with long-chain alkyl radical; and / or with amphoteric surfactants, usually in an amount up to 15 wt .-%, preferably 1 to 10 wt .-%, for example derivatives of secondary or tertiary amines such as. B. C ₆ -C ₁₈ alkyl betaines or C ₆ -C ₁₅ alkylsulfobetaines or alkylamidobetaines or amine oxides such as alkyldimethylamine oxides can be combined.

Cationic surfactants such as those described in WO 99/19435 can also be used are described.

As a rule, the mixtures to be used according to the invention with builders (Sequestering agents) such. B. polyphosphates, polycarboxylates, phosphonates, Complexing agents, e.g. B. methylglycinediacetic acid and its salts, nitrilotriacetic acid and their salts, ethylenediaminetetraacetic acid and their salts and, if appropriate, with co- Combined builders.

Individual builder substances which are well suited for combination with the mixtures to be used according to the invention are listed below:
Suitable inorganic builders are, above all, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as, in particular, zeolites. Different types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially replaced by other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in US-A-4604224.

Suitable crystalline silicates as builders are, for example, disilicates or layered silicates, e.g. B. δ-Na ₂ Si ₂ O ₅ or β-Na ₂ Si ₂ O ₅ . The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates. Amorphous silicates such as sodium metasilicate, which has a polymeric structure, or amorphous disilicate can also be used.

Suitable carbonate-based inorganic builder substances are carbonates and Bicarbonates. These can be in the form of their alkali metal, alkaline earth metal or Ammonium salts are used. Na, Li and Mg carbonates or Hydrogen carbonates, in particular sodium carbonate and / or sodium hydrogen carbonate, used.

Common phosphates used as inorganic builders are Alkali orthophosphates, and / or polyphosphates such. B. pentasodium triphosphate.

The builder components mentioned can be used individually or in mixtures with one another be used.

Furthermore, it is advisable in many cases to add co-builders to the detergents according to the invention. Examples of suitable substances are listed below:
In a preferred embodiment, the detergents according to the invention contain, in addition to the inorganic builders, 0.05 to 20% by weight, in particular 1 to 10% by weight, of organic cobuilders in the form of low molecular weight, oligomeric or polymeric carboxylic acids, in particular polycarboxylic acids, or phosphonic acids or the like Salts, especially Na or K salts.

Examples of suitable low-molecular carboxylic acids or phosphonic acids as organic cobuilders are:
Phosphonic acids such as B. 1-hydroxyethane-1,1-diphosphonic acid, aminotris (methylenephosphonic acid), ethylenediamine-tetra (methylenephosphonic acid), hexamethylenediamine-tetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid);
C ₄ - to C ₂₀ di, tri and tetracarboxylic acids such as. B. succinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ - to C ₁₆ -alkyl or -alkenyl radicals;
C ₄ - to C ₂₀ hydroxycarboxylic acids such. B. malic acid, tartaric acid,
Gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
Aminopolycarboxylic acids such as. B. nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, alkylethylenediamine triacetates, N, N-bis (carboxymethyl) glutamic acid, ethylenediaminedisuccinic acid and N- (2-hydroxyethyl) iminodiacetic acid, methyl- and ethylenediacetic acid, methyl- and ethylacetic acid.

Examples of suitable oligomeric or polymeric carboxylic acids as organic cobuilders are:
Oligomaleic acids as described, for example, in EP-A 451508 and EP-A 396303;
Copolymers and terpolymers of unsaturated C ₄ to C ₈ dicarboxylic acids, the comonomers being monoethylenically unsaturated monomers from group (i) given below in amounts of up to 95% by weight and from group (ii) in amounts of up to 60% by weight and from group (iii) in amounts of up to 20% by weight.

Examples of suitable unsaturated C ₄ to C ₈ dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.

Group (i) includes monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids such as. As acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.

Group (ii) comprises monoethylenically unsaturated C ₂ to C ₂₂ olefins, vinyl alkyl ethers with C ₁ to C ₈ alkyl groups, styrene, vinyl esters of C ₁ to C ₈ carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C ₂ to C ₆ olefins, vinyl alkyl ethers having C ₁ to C ₄ alkyl groups, vinyl acetate and vinyl propionate.

If the polymers of group (ii) contain vinyl esters in copolymerized form, these can also partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are known, for example, from US-A 3887806 and DE-A 43 13 909 known.

Group (iii) comprises (meth) acrylic esters of C ₁ to C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ to C ₈ amines, N-vinylformamide and N-vinylimidazole.

Also suitable as organic cobuilders are homopolymers of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids such as. B. acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid, especially acrylic acid and methacrylic acid,
Copolymers of dicarboxylic acids, such as. B. copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molecular weights of 1000 to 150,000;
Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of acrylic acid for vinyl ester can vary in the range from 30:70 to 70:30;
Copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446, DE-A 44 15 623 and DE-A 43 13 909 are suitable also as an organic cobuilder.

Suitable unsaturated carboxylic acids are, for example, maleic acid, fumaric acid, Itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid as well as mixtures of acrylic acid and maleic acid, in amounts of 40 to 95% by weight, based on the component to be grafted.

Up to 30% by weight, based on the one to be grafted, can additionally be used for the modification Component, other monoethylenically unsaturated monomers are present in copolymerized form. Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).

Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulins or cellulose, protein hydrolyzates and reduced (hydrogenated or hydrated aminated) degraded polysaccharides such as. B. mannitol, sorbitol, aminosorbitol and N-alkylglucamine suitable as well as polyalkylene glycols with molecular weights up to M _w = 5000 such as. B. polyethylene glycols, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyvalent C ₁ - to C ₂₂ alcohols. (see US-A-5756456)

Polyglyoxylic acids suitable as organic cobuilders are described, for example, in EP-B-001004, US-A-5399286, DE-A-41 06 355 and EP-A-656914. The end groups of the Polyglyoxylic acids can have different structures.

Polyamidocarboxylic acids suitable as organic cobuilders and modified Polyamidocarboxylic acids are known for example from EP-A-454126, EP-B-511037, WO-A-94/01486 and EP-A-581452.

As organic cobuilders, use is also made in particular of polyaspartic acids or cocondensates of aspartic acid with further amino acids, C ₄ to C ₂₅ mono- or dicarboxylic acids and / or C ₄ to C ₂₅ mono- or diamines. Particularly preferred are prepared in phosphorus-containing acids, with C ₆ - to C ₂₂ used modified mono- or diamines, polyaspartic acids - to C ₂₂ -mono- or -dicarboxylic acids or with C. ₆

Iminodisuccinic acid are also suitable as organic cobuilders, Oxydisuccinic acid, aminopolycarboxylates, alkyl polyaminocarboxylates, Aminopolyalkylenephosphonates, polyglutamates, hydrophobically modified citric acid such as z. B. agaricic acid, poly-α-hydroxyacrylic acid, N-acylethylenediamine triacetates such as Lauroylethylenediamine triacetate and alkylamides of ethylenediaminetetraacetic acid such as EDTA-tallow amide.

Oxidized starches can also be used as organic cobuilders.

Further suitable (co) builders are described in WO 99/19435.

In a further preferred embodiment, the inventive Detergent in addition, in particular in addition to the inorganic builders, the anionic surfactants and / or the nonionic surfactants, 0.5 to 20% by weight, in particular 1 to 10% by weight, glycine-N, N-diacetic acid derivatives, as described in WO 97/19159 are described.

It is often also expedient to use bleaching systems, consisting of bleaching agents, such as. B. perborate, percarbonate and optionally Bleach activators such. B. tetraacetylethylenediamine, + bleach stabilizers and optionally add bleaching catalysts.

In these cases, the detergents according to the invention additionally contain 0.5 to 30% by weight, in particular 5 to 27 wt .-%, especially 10 to 23 wt .-% bleach in the form of Percarboxylic acids, e.g. B. Diper-oxododecanedicarboxylic acid, phthalimidopercaproic acid or Monoperoxophthalic acid or terephthalic acid, adducts of hydrogen peroxide inorganic salts, e.g. B. sodium perborate monohydrate, sodium perborate tetrahydrate, Sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of Hydrogen peroxide on organic compounds, e.g. B. urea perhydrate, or of inorganic peroxo salts, e.g. B. alkali metal persulfates, or -peroxodisulfates, optionally in combination with 0 to 15% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 8 wt .-%, bleach activators.

• - polyacylierte Zucker, z. B. Pentaacetylglucose;
• - Acyloxybenzolsulfonsäuren und deren Alkali- und Erdalkaiimetallsalze, z. B. Natrium-p-nonanoyloxybenzolsulfonat oder Natrium-p-benzoyloxybenzolsulfonat;
• - N,N-diacylierte und N,N,N',N'-tetraacylierte Amine, z. B. N,N,N',N'- Tetraacetylmethylendiamin und -ethylendiamin (TAED), N,N-Diacetylanilin, N,N- Diacetyl-p-toluidin oder 1,3-diacylierte Hydantoine wie 1,3-Diacetyl-5,5- dimethylhydantoin;
• - N-Alkyl-N-sulfonylcarbonamide, z. B. N-Methyl-N-mesylacetamid oder N-Methyl- N-mesylbenzamid;
• - N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole, z. B. Monoacetylmaleinsäurehydrazid;
• - O,N,N-trisubstituierte Hydroxylamine, z. B. O-Benzoyl-N,N-succinylhydroxylamin, O- Acetyl-N,N-succinylhydroxylamin oder O,N,N-Triacetylhydroxylamin;
• - N,N'-Diacylsulfurylamide, z. B. N,N'-Dimethyl-N,N'-diacetylsulfurylamid oder N,N'-Diethyl-N,N'-dipropionyisulfurylamid;
• - acylierte Lactame wie beispielsweise Acetylcaprolactam, Octanoylcaprolactam, Benzoylcaprolactam oder Carbonylbiscaprolactam;
• - Anthranilderivate wie z. B. 2-Methylanthranil oder 2-Phenylanthranil;
• - Triacylcyanurate, z. B. Triacetylcyanurat oder Tribenzoylcyanurat;
• - Oximester und Bisoximester wie z. B. O-Acetylacetonoxim oder Bisisopropyliminocarbonat;
• - Carbonsäureanhydride, z. B. Essigsäureanhydrid, Benzoesäureanhydrid, m- Chlorbenzoesäureanhydrid oder Phthalsäureanhydrid;
• - Enolester wie z. B. Isopropenylacetat;
• - 1,3-Diacyl-4,5-diacyloxy-imidazoline, z. B. 1,3-Diacetyl-4,5-diacetoxyimidazolin;
• - Tetraacetylglycoluril und Tetrapropionylglycoluril;
  diacylierte 2,5-Diketopiperazine, z. B. 1,4-Diacetyl-2,5-diketopiperazin;
• - ammoniumsubstituierte Nitrile wie z. B. N-Methylmorpholiniumacetonitrilmethylsulfat;
• - Acylierungsprodukte von Propylendiharnstoff und 2,2-Dimethylpropylendiharnstoff, z. B. Tetraacetylpropylendiharnstoff;
• - α-Acyloxypolyacylmalonamide, z. B. α-Acetoxy-N,N'-diacetylmalonamid;
• - Diacyl-dioxohexahydro-1,3,5-triazine, z. B. 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5- triazin;
• - Benz-(4H)1,3-oxazin-4-one mit Alkylresten, z. B. Methyl, oder aromatischen Resten z. B. Phenyl, in der 2-Position;
• - kationische Nitrile, wie in DE-A-101 48 577 beschrieben.

Suitable bleach activators are:

• - polyacylated sugars, e.g. B. Pentaacetylglucose;
• - Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, e.g. B. sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate;
• - N, N-diacylated and N, N, N ', N'-tetraacylated amines, e.g. B. N, N, N ', N'-tetraacetylmethylene diamine and ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5 , 5-dimethylhydantoin;
• - N-alkyl-N-sulfonylcarbonamides, e.g. B. N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide;
• - N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. B. monoacetyl maleic acid hydrazide;
• - O, N, N-trisubstituted hydroxylamines, e.g. B. O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine or O, N, N-triacetylhydroxylamine;
• - N, N'-diacylsulfurylamides, e.g. B. N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionyisulfurylamide;
• acylated lactams such as acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonyl biscaprolactam;
• - Anthranil derivatives such as B. 2-methylanthranil or 2-phenylanthranil;
• - Triacylcyanurate, e.g. B. triacetyl cyanurate or tribenzoyl cyanurate;
• - Oxime esters and bisoxime esters such as. B. O-acetylacetone oxime or bisisopropyliminocarbonate;
• - Carboxylic anhydrides, e.g. B. acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
• - enol esters such as B. isopropenyl acetate;
• - 1,3-diacyl-4,5-diacyloxy-imidazolines, e.g. B. 1,3-diacetyl-4,5-diacetoxyimidazoline;
• - tetraacetylglycoluril and tetrapropionylglycoluril;
  diacylated 2,5-diketopiperazines, e.g. B. 1,4-diacetyl-2,5-diketopiperazine;
• - Ammonium substituted nitriles such as. B. N-methylmorpholinium acetonitrile methyl sulfate;
• - acylation products of propylene diurea and 2,2-dimethylpropylene diurea, e.g. B. tetraacetylpropylene diurea;
• - α-Acyloxypolyacylmalonamide, e.g. B. α-acetoxy-N, N'-diacetylmalonamide;
• - Diacyl-dioxohexahydro-1,3,5-triazines, e.g. B. 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
• - Benz- (4H) 1,3-oxazin-4-one with alkyl radicals, e.g. B. methyl, or aromatic radicals such. B. phenyl, in the 2-position;
• - Cationic nitriles, as described in DE-A-101 48 577.

The described bleaching system consisting of bleaching agents and bleach activators can optionally also contain bleaching catalysts. Suitable bleaching catalysts are for example quaternized imines and sulfonimines, which are described for example in US-A 5 360 569 and EP-A 453 003. Particularly effective bleaching catalysts are Manganese complexes, which are described for example in WO-A 94/21777. Such In the case of their use in detergents, compounds are at most in amounts up to 1.5% by weight, in particular up to 0.5% by weight, in the case of very active Manganese complexes in amounts up to 0.1 wt .-%, incorporated. More suitable Bleaching catalysts are described in WO 99/19435.

Other bleaching systems based on arylimidoperalkanoic acids that can be used are in EP-A-0 325 288 and EP-A-0 490 409.

bleach stabilizer

These are additives that absorb, bind or traces of heavy metals can complex. Examples of additives which can be used according to the invention bleach-stabilizing effect are polyanionic compounds such as polyphosphates, Polycarboxylates, polyhydroxypolycarboxylates, soluble silicates as complete or partially neutralized alkali or alkaline earth salts, especially as neutral Na or Mg Salts that are relatively weak bleach stabilizers. Strong usable according to the invention Bleach stabilizers are, for example, complexing agents such as ethylenediaminetetraacetate (EDTA), nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), β-alanine diacetic acid (ADA), ethylenediamine-N, N'-diesuccinate (EDDS) and phosphonates such as ethylenediaminetetramethylenephosphonate, diethylenetriaminepentamethylenephosphonate or hydroxyethylidene-1,1-diphosphonic acid in the form of the acids or as partial or fully neutralized alkali metal salts. The complexing agents are preferably used in Form of their Na salts used.

In addition to the described bleaching system consisting of bleaching agents, bleach activators and optionally bleaching catalysts is also the detergent according to the invention Use of systems with enzymatic peroxide release or of photo-activated bleaching systems possible, see e.g. B. US 4,033,718.

For a number of applications, it is useful if the invention Detergents contain enzymes. Enzymes are preferably used in detergents Proteases, amylases, lipases and cellulases. Of the enzymes are preferred amounts of 0.1 to 1.5 wt .-%, particularly preferably 0.2 to 1.0 wt .-%, of added enzyme. Suitable proteases are e.g. B. Savinase and Esperase. A suitable lipase is e.g. B. Lipolase. A suitable cellulase is e.g. B. Celluzym. Also the use of peroxidases to activate the bleaching system is possible. you can use single enzymes or a combination of different enzymes. If necessary, the detergent according to the invention can also contain enzyme stabilizers, e.g. B. Calcium propionate, sodium formate or boric acids or their salts, and / or Oxidation preventers included.

The components of detergents are known in principle to the person skilled in the art. The above and the lists of suitable ingredients below give only one exemplary section of the known suitable components again.

In addition to the main components mentioned above, the detergents according to the invention can also contain the following further customary additives in the amounts customary for this:
Known dispersants, such as naphthalenesulfonic acid condensates or polycarboxylates, soil release agents, soil release agents, such as polyether esters, incrustation inhibitors, pH-regulating compounds such as alkalis or alkali donors (NaOH, KOH, pentasodium metasilicate, sodium carbonate) or acids (hydrochloric acid, phosphoric acid, amidosulfonic acid, amidosulfonic acid) such as acetate or phosphate buffer, ion exchangers, perfume, dyes, graying inhibitors, optical (fluorescent) brighteners, color transfer inhibitors such as. B. polyvinylpyrrolidone, biocides such as isothiazolinones or 2-bromo-2-nitro-1,3-propanediol, hydrotropic compounds as solubilizers or solubilizers, such as cumene sulfonates, toluenesulfonates, short-chain fatty acids, urea, alcohols or phosphoric acid alkyl / aryl esters, foam regulators Stabilization or damping of the foam, e.g. As silicone oils, skin and anti-corrosion agents, disinfectant compounds or systems such. B. those which release chlorine or hypochlorous acid such as dichloroisocyanurate or which contain iodine, thickeners and adjusting and confectioning agents.

Graying inhibitors and soil release polymers

Suitable soil release polymers and / or graying inhibitors for detergents are, for example:
Polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids;
Polyester made of polyethylene oxides which are end group-capped with di- and / or polyhydric alcohols and dicarboxylic acid.

Such polyesters are known, for example from US-A 3,557,039, GB-A 1 154 730, EP-A-185 427, EP-A-241 984, EP-A-241 985, EP-A-272 033 and US-A 5,142,020.

Other suitable soil release polymers are amphiphilic graft or copolymers of Vinyl and / or acrylic esters on polyalkylene oxides (cf. US-A 4,746,456, US-A 4,846,995, DE-A-37 11 299, US-A 4,904,408, US-A 4,846,994 and US-A 4,849,126) or modified Celluloses such as B. methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.

Color transfer inhibitors

Examples of color transfer inhibitors are homopolymers and copolymers of Vinyl pyrrolidone, vinyl imidazole, vinyl oxazolidone and 4-vinyl pyridine N-oxide with molecular weights from 15,000 to 100,000 and cross-linked, finely divided polymers based on these Monomers used. The use of such polymers mentioned here is known, cf. DE-B-22 32 353, DE-A-28 14 287, DE-A-28 14 329 and DE-A-43 16 023.

Suitable polyvinylpyridine betaines are e.g. B. in Tai, Formulating Detergents and Personal Care Products, AOCS Press, 2000, page 113.

In addition to use in detergents and cleaning agents for textile laundry in the household the detergent compositions which can be used according to the invention are also in the range commercial textile laundry and commercial cleaning. Usually will In this area of application, peracetic acid is used as a bleaching agent, as an aqueous solution is added to the wash liquor.

Use in laundry detergents

• - 0,5 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-%, mindestens eines anionischen und/- oder nichtionischen Tensids, einschließlich der erfindungsgemäßen Gemische,
• - 0,5 bis 60 Gew.-%, vorzugsweise 15 bis 40 Gew.-%, mindestens eines anorganischen Builders,
• - 0 bis 20 Gew.-%, vorzugsweise 0,5 bis 8 Gew.-%, mindestens eines organischen Cobuilders,
• - 2 bis 35 Gew.-%, vorzugsweise 5 bis 30 Gew.-%, eines anorganischen Bleichmittels,
• - 0,1 bis 20 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, eines Bleichaktivators, gegebenenfalls in Abmischung mit weiteren Bleichaktivatoren,
• - 0 bis 1 Gew.-%, vorzugsweise bis höchstens 0,5 Gew.-%, eines Bleichkatalysators,
• - 0 bis 5 Gew.-%, vorzugsweise 0 bis 2,5%, eines polymeren Farbübertragungsinhibitors,
• - 0 bis 1,5 Gew.-%, vorzugsweise 0,1 bis 1,0 Gew.-%, Protease,
• - 0 bis 1,5 Gew.-%, vorzugsweise 0,1 bis 1,0 Gew.-%, Lipase,
• - 0 bis 1,5 Gew.-%, vorzugsweise 0,2 bis 1,0% Gew.-% eines Soil-Release-Polymers,

ad 100% übliche Hilfs- und Begleitstoffe und Wasser. A typical powder or granular heavy-duty detergent according to the invention can have, for example, the following composition:

• 0.5 to 50% by weight, preferably 5 to 30% by weight, of at least one anionic and / or nonionic surfactant, including the mixtures according to the invention,
• 0.5 to 60% by weight, preferably 15 to 40% by weight, of at least one inorganic builder,
• 0 to 20% by weight, preferably 0.5 to 8% by weight, of at least one organic cobuilder,
• 2 to 35% by weight, preferably 5 to 30% by weight, of an inorganic bleaching agent,
• 0.1 to 20% by weight, preferably 0.5 to 10% by weight, of a bleach activator, optionally in a mixture with other bleach activators,
• 0 to 1% by weight, preferably up to at most 0.5% by weight, of a bleaching catalyst,
• 0 to 5% by weight, preferably 0 to 2.5%, of a polymeric color transfer inhibitor,
• 0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, protease,
• 0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, lipase,
• 0 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of a soil release polymer,

ad 100% usual auxiliary and accompanying substances and water.

Inorganic builders preferably used in detergents are sodium carbonate, Sodium bicarbonate, zeolite A and P as well as amorphous and crystalline sodium silicates as well Phyllosilicates.

Organic cobuilders preferably used in detergents Acrylic acid / maleic acid copolymers, acrylic acid / maleic acid / vinyl ester terpolymers and Citric acid.

Inorganic bleaching agents preferably used in detergents are sodium perborate and sodium carbonate perhydrate.

Anionic surfactants preferably used in detergents are linear and light branched alkyl benzene sulfonates (LAS), fatty alcohol sulfates / ether sulfates and soaps.

Enzymes preferably used in detergents are protease, lipase, amylase and Cellulase. The detergent is usually used in quantities of the commercially available enzymes from 0.05 to 2.0% by weight, preferably 0.2 to 1.5% by weight, of the made-up enzyme added. Suitable proteases are e.g. B. Savinase, Desazym and Esperase. A suitable one Lipases are e.g. B. Lipolase. A suitable cellulase is e.g. B. Celluzym.

Graying inhibitors and soil release agents preferably used in detergents Polymers are graft polymers of vinyl acetate on molecular weight polyethylene oxide 2,500-8,000 in a weight ratio of 1.2: 1 to 3.0: 1, Polyethylene terephthalates / oxyethylene terephthalates with a molecular weight of 3,000 to 25,000 made of polyethylene oxides the molar mass 750 to 5,000 with terephthalic acid and ethylene oxide and a molar ratio from polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and Block polycondensates according to DE-A-44 03 866.

Color transfer inhibitors preferably used in detergents are soluble NVP Homopolymers and / or vinyl pyrrolidone and vinyl imidazole copolymers with molecular weights over 5,000.

The detergents are often in solid, powdered form and then contain in usually additional standard adjusting agents, which give them good flowability, meterability and impart solubility and prevent caking and dusting, such as Sodium sulfate or magnesium sulfate.

The powdered or granular detergents according to the invention can contain up to 60% by weight contain inorganic adjusting agents. The detergents according to the invention are preferably but low in adjusting agents and contain only up to 20% by weight, particularly preferably only up to 8% by weight on positioning devices.

The detergents according to the invention can have different bulk densities in the range of 300 to 1,200, especially 500 to 950 g / l. Have modern compact detergents usually high bulk densities and show a granular structure. Compact or ultra Compact detergents and extrudates have a bulk density> 600 g / l. This are becoming more and more important.

If they are to be used in liquid form, they can be aqueous Microemulsions, emulsions or solutions are present. In liquid detergents can also solvents such as ethanol, i-propanol, 1,2-propylene glycol, or Butyl glycol can be used.

In the case of gel-form detergents according to the invention, thickeners such as, for. B. Polysaccharides and / or weakly cross-linked polycarboxylates (e.g. Carbopol® from Goodrich) are used.

In the case of tablet detergents, tabletting aids such as e.g. B. Polyethylene glycols with molecular weights> 1000 g / mol, polymer dispersions, and Tablet disintegrants such as cellulose derivatives, crosslinked polyvinylpyrrolidone, crosslinked Polyacrylates or combinations of acids, e.g. B. citric acid + sodium bicarbonate, to name just a few.

Another object of the present invention is the use of the mixtures in the production of detergents.

Yet another object of the invention is a washing process using a detergent according to the invention.

The invention is illustrated by the examples below.

Preparation Examples

The alcohol and KOH (finely powdered) are mixed and over at 80 ° C and 40 mbar Drained for 1 hour. The reaction product is placed in an autoclave which Autoclave inerted twice with nitrogen and then heated to 120 ° C. Within 15 Minutes, ethylene oxide is metered in up to a maximum pressure of 1 bar. You hold 5 min at this pressure, the pressure then increases by adding ethylene oxide inside 60 min to 3 bar, lasts for 5 hours at this pressure and finally increases the pressure up to to 6 bar. At the last dosage, only enough ethylene oxide is added until the one below specified amount of ethylene oxide is reached. The pressure is then reduced by adding Nitrogen kept at 6 bar. After a further 10 hours reaction time is on Allow to cool to room temperature and the reaction discharge is filled. At the Rotary evaporators remove volatile components at 30 mbar and 80 ° C.

example 1 2-propylheptanol + 5 EO

There were 474 g of 2-propylheptanol (3.0 mol), 661 g of ethylene oxide (15.0 mol) and 2.3 g KOH used.

Example 2 2-propylheptanol + 7 EO

There were 474 g of 2-propylheptanol (3.0 mol), 925 g of ethylene oxide (21.0 mol) and 2.8 g KOH used.

Example 3 2-propylheptanol + 10 EO

There were 474 g of 2-propylheptanol (3.0 mol), 1,322 g of ethylene oxide (30.0 mol) and 3.6 g KOH used.

Example 4 iso-C13 alcohol 5 EO

There were 401 g of iso-C13 alcohol (2.0 mol), 441 g of ethylene oxide (10.0 mol) and 1.7 g of KOH used.

Example 5 iso-C13 alcohol 7 EO

There were 401 g of iso-C13 alcohol (2.0 mol), 617 g of ethylene oxide (14.0 mol) and 2.0 g of KOH used.

Example 6 iso-C13 alcohol 11 EO

401 g of iso-C13 alcohol (2.0 mol), 969 g of ethylene oxide (22.0 mol) and 2.7 g of KOH were used. applications washing conditions primary laundering device Launder-o-meter from Atlas, Chicago USA wash liquor 250 ml washing time 30 min. at specified temperature (including heating-up time) detergent dosage 4.5 g / l water hardness 3 mmol / l Ca: Mg 4: 1 liquor ratio 1: 12.5 Test fabric Manufacturer wfk 10C wool fat / pigment on cotton wfk Testgewebe GmbH, Brüggen, Germany wfk 10D skin fat / pigment on cotton wfk Testgewebe GmbH, Brüggen, Germany wtk 20D skin fat / pigment on mixed fabric wfk Testgewebe GmbH, Brüggen, Germany wfk 10PF vegetable fat / pigment on cotton wfk Testgewebe GmbH, Brüggen, Germany EMPA 101 olive oil / soot on cotton EMPA test materials, St. Gallen, Switzerland

The washed test fabrics are measured with a Datacolor photometer (Elrepho 2000). The dirt removal is given in percent. The higher the dirt removal, the better the primary washing ability. washing formulation sodium 12.0 Sodium hydroxide monohydrate 14.4% sodium silicate 3.0% sodium sulphate 4.0% Soap 0.5% Copolymer AS / MS 7: 3 5.0% TAED 4.0% carboxymethylcellulose 1.2% Zeolite A 30% surfactants according to the invention as stated water Rest to 100%

R = reflectance value at 460 nm

The results of the wash trials are summarized in the table below.

As can be seen from the results summarized in the table, the operation continues of the alkoxylate mixture according to the invention to a significant improvement in Primary washing effect in the detergent.

Claims (10)

1. Alkoxylate mixture containing
0.1 to 99.9% by weight of at least one alkoxylate of the general formula (I)

C _n H _{2n + 1} O (A) _x (B) _y H (I)

with the meaning
A ethyleneoxy
BC ₃ -C ₁₀ alkyleneoxy or mixtures thereof,
groups A and B can be statistically distributed, alternating or in the form of two or more blocks in any order,
n integer in the range from 8 to 11,
x number in the range from 1 to 20,
y number in the range from 0 to 10, and
0.1 to 99.9% by weight of at least one alkoxylate of the general formula (II)

C _m H _{2m + 1} O (A) _v (B) _w H (II)

with the meaning
A ethyleneoxy
BC ₃ -C ₁₀ alkyleneoxy or mixtures thereof,
groups A and B can be statistically distributed, alternating or in the form of two or more blocks in any order,
m integer in the range from 12 to 24,
v number in the range from 1 to 50,
w Number in the range from 0 to 10. 2. Mixture according to claim 1, characterized in that in the alkoxylate general formula (I) n has the value 10. 3. Mixture according to claim 2, characterized in that in the alkoxylate of the general formula (I) C ₁₀ H _{21 has} the meaning C ₅ H ₁₁ CH (C ₃ H ₇ ) CH ₂ . 4. Mixture according to claim 3, characterized in that in the alkoxylate of the general formula (I)
70 to 99% by weight
Alkoxylates A1 in which C ₅ H _{11 has} the meaning nC ₅ H ₁₁ , and
1 to 30% by weight
Alkoxylates A2 in which C ₅ H _{11 has} the meaning C ₂ H ₅ CH (CH ₃ ) CH ₂ and / or CH ₃ CH (CH ₃ ) CH ₂ CH ₂ ,
are present in the mixture. 5. Mixture according to one of claims 1 to 4, characterized in that in Alkoxylate of the general formula (II) m is an integer in the range from 12 to 18 is. 6. Mixture according to one of claims 1 to 5, characterized in that in Alkoxylate of the general formula (I) x is a number in the range from 3 to 12 and y has the value 0, and in the general formula (II) v has a number in the range from 3 to Is 15 and w is 0. 7. Process for the preparation of alkoxylate mixtures according to one of claims 1 to 6, characterized in that alkanols of the general formula C _n H _{2n + 1} OH and C _m H _{2m + 1} OH with the meaning given for n and m with C _{2- 5} -alkylene oxides are reacted under alkoxylation conditions and mixed with one another before or after the alkoxylation or after a partial alkoxylation. 8. Detergent or cleaning agent containing an alkoxylate mixture according to one of the Claims 1 to 6. 9. washing or cleaning agent according to claim 8, characterized in that the Alkoxylate mixture in an amount of 0.01 to 80 wt .-%, based on the washing or detergent. 10. Use of a detergent or cleaning agent according to claim 8 or 9 for Washing or cleaning textiles.