EP2809642A1 - Alkoxylates of hydrogenated farnesols and use thereof - Google Patents

Abstract

The present invention relates to novel farnesol alkoxylates based on at least partly hydrogenated farnesol; to processes for preparing these alkoxylates and to the use thereof in washing, rinsing, cleaning or conditioning compositions, cosmetic compositions, compositions for papermaking, fuel additives and solubilizing aids in aqueous liquid systems.

Description

 Alkoxylates of hydrogenated farnesols and their use

The present invention relates to novel farnesol alkoxylates based on at least partially hydrogenated farnesol; Process for the preparation of these alkoxylates and their use in washing, rinsing, cleaning or softening compositions, cosmetics, paper-making agents, fuel additives and solubilizing agents in aqueous fluid systems.

Background of the invention

The prior art (see, for example, DE 100 64 491, WO 2001/70384, WO 01/70925, WO 01/70661 and WO 02/24624) discloses the preparation and use of fragrance alcohol alkoxylates, such as, for example, farnesol alkoxylates , in washing, rinsing, cleaning and finishing agents, as well as cosmetic preparations and known as solubilization aids. It does not describe the use of at least partially hydrogenated farnesols as starting material for the preparation of the alkoxylates. Also not described is the preparation of short and medium chain length mixed alkoxylates made up of blocks of different alkoxylates wherein the primary, i.e. alkoxylate block linked to the farnesol is a propoxylate block.

WO 2004/006883 discloses skin care compositions based on branched alcohols having a chain length of at least 7 carbon atoms. Alcohols with a chain length of more than 13 carbon atoms are not disclosed. In addition, the alcohol derivatives described there are characterized by a carboxyl-terminated, optionally alkoxy-containing side group.

The farnesol alkoxylates known from the prior art do not yet fully satisfy the requirements of a practical application in the abovementioned fields, since the threefold unsaturated side chain is less chemically stable and can form various decomposition products in the presence of atmospheric oxygen. It is therefore an object of the present invention to provide novel farnesol alkoxylates with improved property profile. Summary of the invention

The object described above has surprisingly been achieved by providing inventive farnesol alkoxylates of the general formula I in which R is an at least partially hydrogenated farnesyl radical.

Detailed description of the invention A) Definitions

Unless otherwise specified, the following definitions apply within the scope of the present invention.

According to the invention, "farnesol" encompasses all stereoisomeric forms of this compound, including in particular the E / E configurations of the natural farnesol but also the E / Z or Z / E configuration of synthetic farnesols, or mixtures of these configurations The same applies to the hydrocarbon radicals derived from farnesol, hereinafter also referred to as "farnesyl" radicals.

An "at least partially" hydrogenated farnesol or farnesyl radical is understood as meaning compounds or radicals in which one, two or three of the double bonds of the farnesol or of the farnesyl radical are hydrogenated Double hydrogenation (hydrogenation of two of the three double bonds) may also occur in any position The term "at least partially hydrogenated" also encompasses mixtures of partially and completely hydrogenated farnesols or partially and completely hydrogenated farnesyl radicals, in which case additionally unhydrogenated farnesol or Non-hydrogenated farnesyl radicals may also be included.

"Mixtures" of alkoxylates described herein are when individual components differ in terms of meaning of the radical R or the radical (-A-O-) _x . Thus, the x values in the mixture may vary, such as integer values from 0 to 100, 1 to 50, or 1 to 20, in particular 2 to 15, 2 to 10 or 2 to 8, such as, for example, 3, 4, 5, 6, or 7. Particular mention may be made of "narrow-stranded" alkoxylates low degree of distribution. In the mixture, therefore, the parameters x, xl _^ xn on average can also assume non-integer values. The same applies to the parameter "n" (cf., for example, formula (la) below).

The stated degrees of alkoxylation (x values) represent, in particular, statistical average values which, for a specific product, may be an integer or a fractional number.

"Lower alkylene" refers in particular to C 2-12 -alkylene radicals, that is to say straight-chain or mono- or poly-branched hydrocarbon bridging groups having 2 to 12 carbon atoms of the general formula

-CRaRtrCRcRd " stands in which

a, Rb, R _c and Rd are the same or different and these radicals independently of one another are H or a Ci to Cio-alkyl radical which is in particular straight-chain, with the proviso that at least one of the radicals R _a , Rb, Rc and Rd is H and does not exceed the total number of C atoms of the lower alkylene group 12.

In particular, the lower alkylene group may be, for example, C 2 -C 6 -alkylene groups, for example selected from - (CH ₂ ) ₂ -, -CH ₂ -CH (Met) -, -CH (Met) -CH ₂ -, -CH (Met) - CH (Met) -, -C (Met) ₂ -CH ₂ -, -CH ₂ -C (Met) ₂ -, -C (Met) ₂ -CH (Met) -, -CH (Met) -C (Met ) ₂ -, -CH ₂ -CH (Et) -, -CH (Et) -CH ₂ -, -CH (Et) -CH (Et) -, -C (Et) ₂ -CH ₂ -, -CH ₂ -C (Et) ₂ -, -CH ₂ -CH (n-prop) -,

-CH (n-prop) -CH ₂ -, -CH (n-prop) -CH (Met) -, -CH ₂ -CH (n-Bu) -, -CH (n-Bu) -CH ₂ -,

-CH (Met) -CH (Et) -, -CH (Met) -CH (n-prop) -, -CH (Et) -CH (Met) -, -CH (Met) -CH (Et) -, or represent C ₂ -C ₄ -alkylene groups, for example selected from - (CH ₂ ) ₂ -,

-CH ₂ -CH (Met) -, -CH (Met) -CH ₂ -, -CH (Met) -CH (Met) -, -C (Met) ₂ -CH ₂ -, -CH ₂ -C (Met ) ₂ -, -CH ₂ -CH (Et) -, -CH (Et) -CH ₂ -, to name just a few non-limiting examples; where Met is methyl, Et is ethyl, n-prop is n-propyl and n-Bu is n-butyl.

"Niedrigalkylenoxide" are the corresponding epoxide-bridged compounds of the above "lower alkylene" groups, such as C ₂ -C ₂ -, C ₂ -C6-, C ₂ -C ₄ -, C3-C10- or C3-C6 alkylene oxide residues.

"Lower alkylene oxide groups" are the radicals (-AlkO-) formed therefrom by opening the epoxide bridge. "Propylene" in particular represents groups of the formulas -CH ₂ -CH (Met) - or - CH (Met) -CH ₂ -

"Propylene oxide" stands for the corresponding epoxide-bridged compounds of the above "propylene" radicals.

"Propylene oxide" are the radicals formed by opening the epoxide bridge (-PO-).

"Alkali metal salts" or "alkali metal hydroxides" include especially salts of lithium, sodium and potassium.

"Alkaline earth metal salts" or "alkaline earth metal hydroxides" include in particular salts of magnesium. Calcium, strontium and barium. B) Special embodiments

The present invention particularly relates to the following specific embodiments: Farnesol alkoxylates of the general formula I.

R-O - (- A-O-) _x -H (I) wherein simultaneously or independently, in particular simultaneously

R is an at least partially hydrogenated farnesyl radical,

A represents identical or different lower alkylene groups, such as, for example, C ₂ -C 12, C ₂ -C 6, or C ₂ -C ₄ -alkylene, where the polyoxyalkylene radical (-A-O) _x - may consist of one or more different oxyalkylene blocks, and

x is an integer or non-integer value of 1 to 100, such as. 2 to 50, 3 to 25, 3 to 15 or 3 to 10; or x is a non-integer or integer value of 9 to 100 or 10 to 100 or 1 to 100 or 12 to 100 or 13 to 100, e.g. 9 to 50, 10 to 25, 12 to 20 or 12 to 18;

or mixtures of such farnesol alkoxylates.

In particular, the subject matter is also farnesol alkoxylates of the general formula Ia

R-0 - [(- A-O-) x] _n -H (la) where R, A, x are as defined above and n is an integer or non-integer value from 2 to 10, such as 2, 3, 4 , 5, 6, 7, 8, 9 or 10; and mixtures of such compounds.

In general, for formula I and / or formula Ia:

In particular, R can also stand for fully hydrogenated farnesyl.

In particular, R may also be partially hydrogenated farnesyl.

A may in particular stand for ethylene.

 A may in particular stand for C3-alkylene, in particular i-propylene.

A may in particular stand for C ₄ -alkylene.

x may be an even or odd value and may be, in particular, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16,

n may be an even or odd number and may be 1, 2 or 3 in particular.

 (-A-O-) x may stand in particular for an EO block.

 (-A-O-) x may in particular be a C3-alkylene oxide, in particular i-propylene oxide block.

(-AO-) x may in particular be a C ₄ -alkylene oxide block.

- [(- A-O-) x] _n may stand in particular for 2 different alkylene oxide blocks. - [(- A-O-) x] _n may stand in particular for 3 different alkylene oxide blocks. - [(- Α-O-) χ] η may in particular comprise an EO block and a C3-alkylene oxide, in particular i-propylene oxide, block in the order EO-PO or PO-EO. - [(- A-O-) x] _n may in particular be an EO block, a C3-alkylene oxide or PO-, in particular i-propylene oxide block, and an alko block, in the order EO-PO-AlkO or EO-AlkO-PO or PO-EO-AlkO or PO-AlkO-EO or AlkO-

EO-PO or AlkO-PO-EO, wherein when AlkO is a C3 alkylene oxide, adjacent blocks contain different alkylene radicals include (wherein PO for propylene oxide, in particular for i-propylene oxide, EO for ethylene oxide and AlkO for a C3-Cio Alkylene oxide block). Farnesol alkoxylates according to embodiment 1, wherein R is a (cis) radical of the formula II

(Met) ₂ C = CH-CH2-CH2-C (Met) = CH-CH2-CH2-C (Met) = CH-CH2- (II) 3 2 1

stands in which

one of the double bonds in positions 1, 2 or 3, or

two of the double bonds in positions 1, 2 or 3, or

all three double bonds in positions 1, 2 and 3,

are hydrogenated; or

wherein R is a mixture of such partially or fully hydrogenated radicals, optionally additionally containing non-hydrogenated farnesyl radicals;

or mixtures of such farnesol alkoxylates.

Farnesol alkoxylates according to one of the preceding embodiments, in which a) the group - (- A-O) _x - represents a polyoxyalkylene radical,

in which simultaneously or independently of one another, at least x for a value of 3 to 50, e.g. 3 to 25 or 4 to 10; and

 Each represents the same lower alkylene groups as e.g. C2-12, C2-6, or C2-4

Alkylene;

or

 A has different meanings and represents at least two different lower alkylene groups, such as e.g. at least two different C1-6, or C1-4 or C2-6, or C2-4-alkylene groups randomly distributed across the polyoxyalkylene moiety;

-A-O- stands in particular for EO, PO or AlkO according to the above definition x stands in particular for 3 to 25

For example, x is 4, 5, 6, 7, 8, 9 or 10.

or b) the polyoxyalkylene radical - (- A-O) _x - from n, such as, for example, 2, 3, 4, 5 or 6, oxyalkylene blocks - (- Ai-0) _x i- to - (- A _n -O) _xn - is constructed, wherein x is equal to the sum x1 + ... + xn and at least two oxyalkylene blocks in terms of meaning of the alkylene radicals (Ai .... A _n ) and / or in terms of the number of their monomer units

(x1 .... xn) and where x1 to xn are independently integer values from 1 to 50, e.g. 2 to 50, 3 to 25, 3 to 15 or 3 to 10; In this case, n stands in particular for 2, 3 or 4.

x1 to xn are independently of each other, for example, 3, 4, 5, 6, 7, 8, 9 or 10.

 -A-O- stands in particular for EO, PO or AlkO as defined above,

or mixtures of such farnesol alkoxylates.

Farnesol alkoxylates according to embodiment 3, wherein the polyoxyalkylene radical is composed of different oxyalkylene blocks and is selected from the radicals:

- (PO) xi- (EO) x2- (AlkO) x ₃ -H

in which, simultaneously or independently of one another, at the same time PO is propylene oxide, EO is ethylene oxide and AlkO is C 3 -C 10 -alkylene oxide, x1 is an integer value of 1, 2 or 3;

x2 is an integer value of 3 to 50, such as. 3 to 20, 3 to 10 or 4 to 8; and

x3 is an integer value of 1 to 10, such as 2 to 9, or 5 to 8; or mixtures of such farnesol alkoxylates.

Farnesol alkoxylates according to embodiment 4, wherein simultaneously or independently of each other, especially at the same time

x1 is an integer value of 1 or 2;

x2 stands for an integer value of 6 to 9, in particular 7 or 8; and

x3 is an integer value of 1 to 5;

or mixtures of such farnesol alkoxylates.

Process for the preparation of a compound of the general formula I

R-0 - (- A-0-) _x -H (I) where you are

a) an alcohol of the general formula III

R-OH (III) in which R has the abovementioned meanings, alkoxylated in the presence of an alkoxylation catalyst, in the presence or absence of a solvent and in the presence of at least one lower alkylene oxide or lower alkylene oxide mixture, to give a compound of formula I,

wherein the group - (- A-O) _x - represents a polyoxyalkylene radical wherein simultaneously or independently of one another, especially simultaneously

x for a value of 3 to 50, e.g. 3 to 20, 3 to 10 or 4 to 8, and A is the same lower alkylene groups; or

 A has different meanings and for at least two different lower alkylene groups, which are randomly distributed over the polyoxyalkylene radical; or b) an alcohol of the general formula III

R-OH (III) in which R has the abovementioned meanings, alkoxylated in the presence of an alkoxylation, in the presence or absence of a solvent and in the presence of a first Niedrigalkylenoxids, and the alkoxylation repeated alternation of the lower alkylene oxide (nl), where n is an integer value (such as from 1 to 10),

wherein a compound of formula I is obtained, wherein the polyoxyalkylene radical

- (- AO) x- is constructed of n oxyalkylene blocks - (- Ai-0) _x i - - (- A _n -0) _xn -, where x is equal to the sum x1 + ... + xn and at least two oxyalkylene respect importance of alkylene radicals (Ai ... A _n) and / or with regard to the number of monomer units (x1 xn) are different and wherein x1 to xn are independently integers from 1 to 50, such as 3 to 20, 3 to 10 or 4 to 8, are.

Process according to embodiment 6 b), wherein

i) the alcohol of the above formula III in the presence of an alkali or alkaline earth metal hydroxide, such as NaOH or KOH, or a multimetal cyanide catalyst and in the presence or absence of a solvent and in the presence of propylene oxide to a propoxylate of formula IV

R-0- (PO) xi-H (IV) propoxylated, and then ii) the propoxylate so formed with the addition of one of the following blocks further alkoxylated;

where x1 to x3 are independently integer values of 1 to 50, e.g. 3 to 20, 3 to 10 or 3 to 8 are.

 Stage i) and ii) can be carried out with or preferably without a catalyst change.

Process according to embodiment 7, wherein the multimetal cyanide catalyst is selected from catalysts comprising at least one dimetal cyanide compound of general formula (D) in which

M ^{1 is} a metal ion selected from the group consisting of Zn (II), Fe (II), Co (III), Ni (II), Mn (II), Co (II), Sn (II), Pb (II), Fe (III), Mo (IV), Mo (VI), Al (III), V (IV), V (V), Sr (II), W (IV), W (VI), Cu (II) and Cr (III),

M ^{2 is} a metal ion selected from the group consisting of Sr (I), Mg (II), Zn (II), Fe (II), Fe (III), Co (III), Cr (III), Mn (II), Mn (III), Ir (III), Rh (III), Ru (II), V (IV), V (V),

Co (II), Cr (II), Ti (IV),

X is a non-cyanide group which forms a coordinate bond to M ¹ selected from the group consisting of carbonyl, cyanoate, isocyanate, nitrite, thiocyanate and nitrosyl,

a, b, r, t are integers chosen to satisfy the electroneutrality condition. The method of embodiment 8, wherein M ^{1 is} Zn (II) and M ^{2 is selected} from Co (III) and Fe (III). Use of at least one compound according to one of embodiments 1 to 5 in washing, rinsing, cleaning or softening agents; in cosmetic products; in fuels or fuel additive mixtures in agrochemical compositions; or in papermaking equipment. Agents selected from washing, rinsing, cleaning and finishing agents; cosmetic products; Preparations for making paper; agrochemical composition tongues or fuels or fuel additive mixtures containing at least one compound according to one of embodiments 1 to 5.

Process selected from washing, rinsing, cleaning or softening processes; Process for papermaking; or process for the preparation of agrochemical compositions; Fuels or fuel additive mixtures, wherein at least one compound according to one of embodiments 1 to 5 is used in this method.

Use of a compound according to any one of embodiments 1 to 5 as a solubilizing agent in aqueous systems / liquids, in particular in emulsion polymerization.

The invention also provides the process products obtained by a process of embodiments 6 to 9 and their use, as defined above.

C) Preparation of the compounds The farnesol alkoxylates of the formula (I) according to the invention can be prepared in a manner known per se and using conventional equipment.

For example, one suitable method of preparation involves the reaction of an at least partially hydrogenated farnesol in a reactor which, under suitable conditions, is reacted with at least one alkylene oxide, i. with a single alkylene oxide, a mixture of alkylene oxides or stepwise reacted with identical or different alkylene oxides until the desired chain length and / or alkylene oxide block sequence is reached. Before carrying out the reaction, it may be convenient to use the reaction mixture by applying a vacuum and, if appropriate, applying elevated temperature, such as a temperature of 80 to 150 ° C, e.g. 0.1 to 2 h or 0.5 to 1 h. Furthermore, it may be expedient to render the reaction medium inert by exposure to nitrogen.

The reaction is usually carried out in the presence of a suitable alkoxylation catalyst, such as an alkali metal hydroxide, or a Doppelmetallcyanidkataly- sators suspended in a suitable inert organic solvent, such as tridecanol N, at a temperature ranging from room temperature to about 200 ° C, as for example 100 to 180 ° C or 120 to 160 ° C. The reaction can be carried out at atmospheric pressure or an overpressure of up to 100 bar, such as at a pressure in the range of 1 to 50 orl, 5 to 20 or 2 to 10 bar. For example, the molar ratio of at least partially hydrogenated farnesol to alkylene oxide can range from 1: 3 to 1: 100, such as 1: 4 to 1:20 or 1: 5 to 1:10. The reaction time of the actual alkoxylation can then be in the range of one minute to 20 hours, such as 10 minutes to 5 hours. After completion of the reaction and neutralization, for example by addition of acetic acid, the product can be removed from the reactor. D) Applications

The farnesyl alkoxylates according to the invention are used in different "compositions" or "preparations", these terms being understood in the broadest sense and include preparations in solid form (particles, powders, etc.), semi-solid form (pastes, etc.), liquid form (solutions, emulsions , Suspensions, gels, etc.) and gas-like form (aerosols, etc.) which, with regard to an advantageous effect of the farnesyl alkoxylates, usually contain further components customary for the particular application

The aforementioned farnesyl alkoxylates according to the invention can be added according to the invention to washing, rinsing, cleaning and softening compositions. These usually contain one or more of the inventive farnesyl alkoxylates in an amount of 0.001 to 10% by weight, e.g. in an amount of 0, 01 to 5 wt .-%, or in an amount of 0, 02 to 3 wt .-% or 0, 05 to 2 wt%, based on the total weight of the washing, rinsing, Cleaning or avivage agents.

In addition, other ingredients may be included that further improve the performance and / or aesthetic properties of the washing, rinsing, cleaning and softening agents. For example, as further ingredients may be one or more substances selected from enzymes, surfactants and the group of builders, complexing agents, bleaching agents, bleach activators, electrolytes, nonaqueous solvents, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, Silicone oils, anti redeposition agents, dispersants, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, antioxidants, corrosion inhibitors, Antistatic agents, ironing aids, repellents and impregnating agents, swelling and lubricating agents and UV absorbers.

Complexing agents are, for example, methylglycinediacetic acid (MGDA), ethylenediaminetriacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriamine pentaacetic acid (DTPA), tartaric acid, citric acid, glucuronic acid and glycolic acid, and the salts of these compounds.

The enzymes are preferably selected from hydrolases, such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannanases, pectate lyases, other glycosyl hydrolases and mixtures of the abovementioned enzymes. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens.

Suitable hydrolases are e.g. α-glucosidases (EC number 3.2.1.20), β-glucosidases (Ovozyme, EC number 3.2.1.21), amylases (Purastar, Termamyl, Stainzyme, Duramyl), mannanases (Purabrite, Mannastar, Mannaway) and cellulases ( Carezyme, Celluzyme, Endolase, Puradax). Suitable amylases include, in particular, α-amylases (EC No. 3.2.1 .1), iso-amylases and pullulanas. Also to be mentioned are glycosidases (EC number 3.2.1 .15), such as pectinases and pectate lyases (EC number 4.2.2.2). The cellulases used are preferably cellobioholrolases, endoglucanases and β-glucosidases, which are also called cellobiases. or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by means of targeted mixtures of the cellulases.

Suitable lipases are esterases, such as Lipex and Lipolase. Examples of lipolytic enzymes are also the known cutinases.

Peroxidases or oxidases have also proved suitable in some cases.

For example, an enzyme mixture may also be included. Enzyme mixtures which contain or consist of the following enzymes are preferred:

Protease and amylase, Protease and lipase (or lipolytic enzymes),

 Protease and cellulase,

 Amylase, cellulase and lipase (or lipolytic enzymes),

 Protease, amylase and lipase (or lipolytic enzymes)

- Protease, lipase (or lipolytic enzymes) and cellulase.

Preferred proteases in the aforementioned mixtures are subtilisin-type proteases (Savinase, etc .; EC No. 3.4.21.62). The enzymes may be adsorbed to carriers to protect them against premature degradation. The proportion of the enzymes is preferably 0.1 to 5 wt .-%, particularly preferably 0.15 to 2.5 wt .-%, in particular 0.2 to 2 wt .-%, based on the total weight of the detergent or cleaning composition , As surfactants it is possible to use anionic, nonionic, cationic and / or amphoteric surfactants, as well as mixtures, for example of anionic and nonionic surfactants. The total surfactant content on average may be 5 to 60% by weight, such as 15 to 40% by weight, based on the total weight of the composition. Examples of nonionic surfactants used are alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 20, such as 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably 2 Position may be methyl-branched or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C ₁₂ -Ci4-alcohols with 3 EO, 7 EO or 4 EO, Ce-Cn-alcohol with 7 EO, C13-C15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ₂ -C ₈ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Ci2-Ci4 alcohol containing 3 EO and C12 CI8 alcohol containing 7 EO. Also to be mentioned are the corresponding alkoxylates of Guerbet alcohols, in particular 2-propylheptanol. The stated degrees of ethoxylation represent statistical averages which may be an integer or a fractional number for a particular product. Also suitable are alcohol ethoxylates which have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO or 30 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated Nio surfactants can be used in which EO and PO units are not distributed blockwise, but statistically distributed. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula (1)

R ¹ 0 (G) i; x (1) can be used, wherein R ^{1 is} a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 10 to 18 carbon atoms and G is a Glykosideinheit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.

Another class of preferred nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (2),

wherein R ^{2 is} C (= O) for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{3 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. In the case of the polyhydroxy fatty acid amides they are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (3)

wherein R ^{4 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{5 is} a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene radical having 6 to 8 carbon atoms and R ^{6 is} a linear, branched or is cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C 1 -C 4 -alkyl or phenyl radicals, and [Z] ^{1 being} a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups , or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] ¹ is preferably obtained by reductive amination of a sugar, for example glucose, fructose, malactose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted, for example, according to WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides. The content of nonionic surfactants in the liquid detergents or cleaners is preferably 0 to 30% by weight, preferably 0 to 20% by weight and in particular 2 to 15% by weight, based in each case on the total weight of the detergent composition. As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Preferred surfactants of the sulfonate type are C 9 -C 13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, such as are obtained, for example, from C 12 -C 18 -monoolefins having an end or internal double bond by sulfonation with gaseous sulfur - feltrioxid and subsequent alkaline or acidic hydrolysis of the sulfonation receives te, into consideration. Also suitable are alkanesulfonates which are obtained from C 12 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters secondary Alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. From a washing-technical point of view, preference is given to the C 12 -C 16 -alkyl sulfates and C 12 -C 18 -alkyl sulfates and also to C 14 -C 18 -alkyl sulfates. Also, 2,3-alkyl sulfates, which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

Also, the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C7-C2i alcohols, such as 2-methyl-branched Cg-Cn alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci2-Ci8 fatty alcohols with 1 up to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Ce-Cie fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols. In turn, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols having a narrower homolog distribution are again particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the AI k (en) yl chain or salts thereof.

Particularly preferred anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids. The anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di-triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. The content of anionic surfactants (including the soaps) is e.g. From 2 to 50% by weight, such as from 3 to 40% by weight, based in each case on the total weight of the composition.

The viscosity of the liquid medium can be measured by conventional standard methods (for example Brookfield LVT-II at 20 rpm and 20 ° C., spindle 3) and is preferably in the range of 100 to 5000 mPas. Preferred agents have viscosities from 300 to 4000 mPas, with values between 1000 and 3000 mPas being particularly preferred. As builders or builders which may be present in the compositions, in particular silicates, aluminum silicates (in particular zeolites) and carbonates and mixtures of these substances may be mentioned. However, the use of such builders is not preferred. As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgC in the compositions is preferred. The proportion of electrolytes is usually 0.5 to 5 wt .-%, based on the total weight of the composition.

The agent according to the invention or used for the inventive use can contain at least one solvent. Suitable solvents are selected from water, non-aqueous solvents and mixtures thereof. Non-aqueous solvents used are preferably nonaqueous organic solvents. Preferred non-aqueous organic solvents are those which are completely miscible with water under normal conditions (20 ° C, 1013 mbar). The solvent content of the detergent or cleaner composition is preferably from 5 to 95% by weight, more preferably from 10 to 80% by weight, based on the total weight of the composition.

Non-aqueous solvents that can be used are derived, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the given concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propylene ether, ethylene glycol mono-n butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, i-butoxyethoxy-2 propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Non-aqueous solvents can be used in amounts of between 0.5 and 15% by weight, but preferably below 12% by weight and in particular below 9% by weight. To bring the pH of the liquid agent within the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 7% by weight, based on the total weight of the detergent composition.

In order to improve the aesthetic impression of the agents, they can be dyed with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, possess a high storage stability and insensitivity to the other ingredients of the compositions and to light, as well as no pronounced substantivity towards textile fibers in order not to stain them.

Suitable foam inhibitors which can be used are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.

Suitable anti-redeposition agents, which are also referred to as "soil repellents", are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case on the nonionic cellulose ether. Suitable soil-release polymers are, for example, polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acid. carboxylic acids or aromatic and aliphatic dicarboxylic acids; Polyesters of unilaterally end-capped polyethylene oxides with dihydric and / or polyhydric alcohols and dicarboxylic acid, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers. Such polyesters are known, for example from US 3,557,039, GB-A 1 1 54 730, EP-A 0 185 427, EP-A 0 241 984, EP-A 0 241 985, EP-A 0 272 033 and US-A 5,142,020 , Further suitable soil-release polymers are amphiphilic graft copolymers or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (compare US Pat. Nos. 4,746,456, 4,846,995, DE-A 37 1 1 299, 4,904,408, 4,846,994 and 4,849,126) or modified Celluloses such as methylcellulose, hydroxypropylcellulose or carboxymethylcellulose.

Optical brighteners (so-called "whiteners") may be added to the compositions to eliminate graying and yellowing of the treated fabrics. These substances are absorbed by the fiber and cause lightening and fake bleaching by converting invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence and the yellowish or yellowed Wash pure white results. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as the heterocyclic-substituted pyrene derivatives. The optical brighteners are usually used in amounts of between 0.03 and 0.3 wt .-%, based on the finished composition.

Dispersants, in particular polycarboxylates (for example SOKALANE from BASF SE) are to be mentioned as further suitable additives.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, preference is given to cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxy methylcellulose and mixtures thereof in amounts of 0.1 to 5 wt .-%, based on the means used.

Since fabrics, particularly rayon, rayon, cotton and blends thereof, can tend to wrinkle because the individual fibers are susceptible to flexing, buckling, squeezing and squeezing across the grain, the compositions may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty alkylol esters, fatty alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

For controlling microorganisms, the agents may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, germicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate.

To prevent undesirable changes in the agents and / or the treated fabrics caused by oxygen and other oxidative processes, the agents may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased comfort may result from the additional use of antistatic agents added to the compositions. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatics are described, for example, in patent applications FR 1, 156,513, GB 873,214 and GB 839,407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed herein are useful as antistatics for textile fabrics or as an additive to laundry detergents, with a softening effect being additionally achieved. To improve the water absorption capacity, the rewettability of the treated fabrics and to facilitate the ironing of the treated fabrics, for example, silicone derivatives can be incorporated in the compositions. be set. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.

Finally, the agents may also contain UV absorbers which are applied to the treated fabrics and improve the lightfastness of the fibers. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid. Liquid agents have no sediment and may be e.g. be transparent or at least translucent. For example, the aqueous liquid agents have a visible light transmittance of at least 30%, preferably 50%, more preferably 75%, most preferably 90%. Alternatively, the thickeners according to the invention can be incorporated into opaque washing or cleaning agents.

In addition to these ingredients, an aqueous medium may contain dispersed particles whose diameter is 0.01 to 10,000 μηη along their greatest spatial extent.

Particles may be microcapsules as well as granules, compounds and fragrance beads, with microcapsules being preferred.

The term "microcapsule" is understood to mean aggregates which contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell of polymer (s). These are usually finely dispersed liquid or solid phases coated with film-forming polymers, during the production of which the polymers precipitate on the material to be enveloped after emulsification and coacervation or interfacial polymerization. The microscopic capsules can be dried like powder. Besides mononuclear microcapsules, multinuclear aggregates, also called microspheres, are known, which contain two or more cores distributed in the continuous shell material. One or Polynuclear microcapsules may also be enclosed by an additional second, third, etc. shell. Preferred are mononuclear microcapsules with a continuous shell. The shell may be made of natural, semi-synthetic or synthetic materials. Natural shell materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, for example sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, sucrose and waxes. Semisynthetic shell materials include chemically modified celluloses, in particular cellulose esters and ethers, for example cellulose acetate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, and also starch derivatives, in particular starch ethers and esters. Synthetic envelope materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone. Inside the microcapsules sensitive, chemically or physically incompatible and volatile components (= active ingredients) of the aqueous liquid detergent or cleaning agent can be trapped stable storage and transport. The microcapsules may include, for example, optical brighteners, surfactants, complexing agents, bleaches, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, graying inhibitors, anti redeposition agents, pH adjusters, electrolytes, foam inhibitors and UV absorbers are located.

The microcapsules may further contain cationic surfactants, vitamins, proteins, preservatives, detergency boosters or pearlescing agents. The fillings of the microcapsules may be solids or liquids in the form of solutions or emulsions or suspensions.

The microcapsules may have any shape in the production-related framework, but they are preferably approximately spherical. Their diameter along their greatest spatial extent, depending on the components contained in their interior and the application between 0.01 μηη (visually not recognizable as a capsule) and 10 000 μηη. Preference is given to visible microcapsules having a diameter in the range from 100 μm to 7000 μm, in particular from 400 μm to 5 000 μm. The microcapsules are accessible by known methods, coacervation and interfacial polymerization being the most important. Suitable microcapsules are all surfactant-stable microcapsules available on the market, for example the commercial products (the shell material is indicated in parentheses) Hallcrest microcapsules (gelatin, gum arabic), coletica thalaspheres (marine collagen), lipotec millicapsules (alginic acid, agar). Agar), Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropyl methylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified Agar Agar) and Kuhs Probiol Nanospheres (phospholipids). Alternatively, it is also possible to use particles which have no core-shell structure but in which the active substance is distributed in a matrix of a matrix-forming material. Such particles are also referred to as "speckies".

A preferred matrix-forming material is alginate. To produce alginate-based speckles, an aqueous alginate solution, which also contains the active ingredient to be enclosed or the active ingredients to be enclosed, is dripped off and then cured in a precipitation bath containing Ca ²⁺ ions or Al ³⁺ ions.

Alternatively, other, matrix-forming materials can be used instead of alginate. Examples of matrix-forming materials include polyethylene glycol, polyvinylpyrrolidone, polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextran, ficoll®, starch, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropyl pylmethylcellulose, hyaluronic acid, carboxymethylcellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials. The matrix formation takes place with these materials, for example via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions. The production of particles with these matrix-forming materials is known per se.

The particles can be stably dispersed in the aqueous liquid detergent or cleaner. Stable means that the compositions are stable at room temperature and at 40 ° C. for a period of at least 4 weeks, and preferably of at least 6 weeks, without the medium creaming or sedimenting. Due to the increase in viscosity, the thickeners according to the invention bring about a kinetic slowing down of the sedimentation of the particles and thus their stabilization in the suspended state. The release of the active ingredients from the microcapsules or speckles is usually carried out during the application of the agents containing them by destruction of the shell or the matrix due to mechanical, thermal, chemical or enzymatic action. The compositions according to the invention can be used for cleaning textile surface fabrics and / or hard surfaces. Detergents according to the invention may be in the form of a hand or machine dishwashing detergent, all-purpose cleaner for non-textile surfaces, eg of metal, lacquered wood or plastic, or detergents for ceramic products, such as porcelain, tiles, tiles. The detergents or cleaners according to the invention are preferably in the form of a liquid laundry detergent. These can be formulated solid, liquid or pasty. D2) Cosmetic agents

Preparations according to the invention may also be cosmetic preparations which differ in their composition from washing, rinsing, cleaning and softening agents according to the preceding description. This applies in particular to non-surfactant cosmetic preparations. However, surfactant-containing cosmetic preparations are also included according to the invention. Preferably, these cosmetic agents contain farnesyl alkoxylates in an amount of 0.001 to 10 wt .-%, preferably in an amount of 0, 01 to 5 wt .-%, such as in an amount of 0, 02 to 3 or in one Amount from 0, 05 to 2 wt .-%, each based on the cosmetic product.

For example, the cosmetic agents are aqueous preparations which optionally contain surfactants or surface-active agents and which are particularly suitable for the treatment of keratin fibers, in particular human hair, or for the treatment of human skin.

For the most important ingredient group, the surface-active (surfactant) active ingredients or washing active ingredients, predominantly fatty alcohol polyglycol ether sulfates (ether sulfates, alkyl ether sulfates) are used, in part in combination with other, usually anionic surfactants. Shampoo surfactants should have a good cleansing power and resistance to water hardness skin and mucous membrane compatibility. According to the legal regulations a good biodegradability should be given. In addition to the alkyl ether sulfates, the agents may additionally contain other surfactants, such as alkyl sulfates, alkyl ether carboxylates, preferably with degrees of ethoxylation of from 4 to 10, and surfactant protein-fatty acid condensates. Here, in particular, the protein-abietic acid condensate should be mentioned. Sulphosuccinic acid esters, amidopropylbetaines, amphoacetates and amphodiacetates, as well as alkyl polyglycosides, are also preferred surfactants in hair shampoos.

Another group of ingredients is summarized under the term excipients and is very diverse: For example, add additives of non-ionic surfactants such as ethoxylated sorbitan esters or protein hydrolysates increase the compatibility or have an anti-irritant, z. In baby shampoos; serve as a refatting to prevent excessive degreasing in the hair wash z. Natural oils or synthetic fatty acid esters; Glycerol, sorbitol, propylene glycol (see propanediols), polyethylene glycols and other polyols serve as humectants. To improve wet combability and reduce electrostatic charge on the hair after drying, cationic surfactants, such as, for example, can be added to the shampoos. B. quaternary ammonium compounds are added. For a colored, brilliant appearance, dyes or pearlescent pigments are added. To set the desired viscosity thickeners of different classes can be used, a pH stability is by buffer z. B. based on citrate, lactate or phosphate. To ensure sufficient shelf life and shelf life, preservatives such. B. 4 Hydroxybenzoesäureester added; Oxidation-sensitive ingredients can be protected by the addition of antioxidants such as ascorbic acid, butylmethoxyphenol or tocopherol.

A third group of ingredients form special ingredients for special shampoos, eg. As oils, herbal extracts, proteins, vitamins and lecithins in shampoos for fast-greasy, especially dry, damaged or damaged hair. Active substances in shampoos for controlling dandruff usually have a broad growth-inhibiting effect against fungi and bacteria. In particular, the fungistatic properties z. B. of pyrithione salts could be detected as the cause of good anti-dandruff action. To produce a pleasant fragrance, the hair shampoos contain perfume oils and / or perfumes. In this case, all the usual, and approved in hair shampoos fragrances can be used.

The aim of hair care products is to preserve the natural state of the newly regrown hair for as long as possible and to restore it when damaged. Characteristics that characterize this natural state are silky shine, low porosity, tension-rich yet soft body and pleasantly smooth feeling. An important prerequisite for this is a clean, dandruff-free and not over-greasy scalp. To the hair products one counts today a multiplicity of different products, whose most important representatives are called pre-treatment means, hair lotions, Frisierhilfsmittel, hair rinses and Kurpackungen, and their composition as with the shampooing agents roughly into basic materials, auxiliary materials and special active substances is divided.

The basic substances used are fatty alcohols, in particular cetyl alcohol (1-hexadecanol) and stearyl alcohol (1-octadecanol), waxes such as beeswax, wool wax (lanolin), spermaceti and synthetic waxes, paraffins, petrolatum, paraffinol and especially ethanol as solvent, 2 -Propanol and water. Excipients are emulsifiers, thickeners, preservatives, antioxidants, dyes and perfume oils. The most important group of special active ingredients in hair care products today are the quaternary ammonium compounds. A distinction is made between monomeric (for example alkyltrimethylammonium halide with, in particular, the lauryl, cetyl or stearyl group as alkyl radical) and polymeric quaternary ammonium compounds [eg. Example: quaternary cellulose ether derivatives or poly (N, N-dimethyl-3, 4-methylenpyrrolidiniumchlorid)]. Their effect in hair care products is based on the fact that the positive charge of the nitrogen atoms of this compound can be attached to the negative charges of hair keratin; Damaged hair contains more negatively charged acid groups due to its higher cysteic acid content and can therefore absorb more quaternary ammonium compounds. These, because of their cationic character, are also known as "cationic care substances". It has a smoothing effect on the hair, improves combability, reduces electrostatic charge, improves grip and shine. The polymeric quaternary ammonium compounds adhere so well to the hair that their effect can be detected even after several washes. Organic acids such as citric acid, tartaric acid or lactic acid are frequently used to set an acidic environment. The water-soluble protein hydrolysates attract well on the hair keratin because of their close chemical relationship. The largest group of special active ingredients in hair care products form various plant extracts and vegetable oils, which have mostly been used for a long time, without their efficacy being scientifically proven in all cases to the stated effect. Likewise, the effectiveness of vitamins used in hair care products is only proven in isolated cases. To avoid over-refatting, some hair lotions contain substances such as certain tar constituents, cysteic acid derivatives or glycyrrhizin; the intended reduction in sebaceous gland production is also not yet clearly established. In contrast, the effectiveness of anti-dandruff agents is well documented. They are therefore used in appropriate hair lotions and other care products.

The aqueous preparations for the treatment of skin are, in particular, preparations for the care of human skin. This care begins with the cleansing for which soaps are primarily used. Here one distinguishes solid, mostly lumpy and liquid soap. Accordingly, in a preferred embodiment, the cosmetic preparations are in the form of shaped bodies which contain surface-active (surface-active) ingredients.

The most important ingredients of such moldings are in a preferred embodiment, the alkali metal salts of the fatty acids of natural oils and fats, preferably with chains of 12 to 18 carbon atoms. Since lauric acid soaps foam particularly well, the lauric acid-rich coconut and palm kernel oils are preferred raw materials for the production of fine soap. The Na salts of the fatty acid mixtures are solid, the K salts soft-pasty. For saponification, the dilute soda or potash liquor is added to the fat raw materials in a stoichiometric ratio so that an excess of caustic solution of max. 0, 05% is present. In many cases, the soaps are no longer produced directly from the fats, but from the fatty acids obtained by lipolysis. Typical soap additives are fatty acids, fatty alcohols, lanolin, lecithin, vegetable oils, partial glycerides and other fat-like substances for moisturizing the cleansed skin, antioxidants such as ascorbyl palmitate or tocopherol for preventing the autoxidation of the soap (rancidity), complexing agents such as nitrilotriacetate for binding Heavy metal traces that could catalyze autoxidative spoilage, perfume oils to obtain the desired fragrance notes, dyes to color the soap bars, and possibly special additives. The most important types of fine soaps are: - Toilet soaps with 20 to 50% coconut oil in the fat mixture, up to 5% Rückfetter-share and. 0, 5 to 2%. Perfume oil, they make up the largest proportion of fine soaps; Luxury soaps with up to 5% z. T. especially precious perfume oils; -Dose soaps with additives of deodorizing agents such. B. 3, 4, 4 'trichlorocarbanilide (triclocarban); -Cream soaps with especially high levels of moisturizing and creaming substances; -Baby soaps with good refatting and additional nourishing shares such. B. chamomile extracts, at best very poorly perfumed; - Skin protection soaps with high levels of moisturizing substances and other nourishing and protective additives, such as. Proteins; Transparent soaps with additions of glycerine, sugars and others, which prevent the crystallization of the fatty acid salts in the solidified soap melt and thus produce a transparent appearance; - Floating soaps with density <1, caused by controlled air bubbles during manufacture. Soaps can also be provided with abrasive additives to clean heavily soiled hands. When washing with soap, the pH in the wash liquor is from 8 to 10. This alkalinity neutralises the natural acid mantle of the skin (pH 5 to 6). Although this is regressed relatively quickly in normal skin, it can cause irritation in sensitive or damaged skin. Another disadvantage of soaps is the formation of insoluble lime soaps in hard water. These disadvantages are not present in syndet soaps. It is based on synthetic anionic surfactants that can be processed into scaffolding substances, refills and other additives to soap-like pieces. Their pH can be varied within wide limits and is usually adjusted to pH 5 or 5, adjusted to neutral pH 7 or the acid mantle of the skin. They have excellent cleaning power, foam in any water hardness, even in seawater, the proportion of lubricating additives must be significantly higher than normal soaps because of their intensive cleaning and degreasing effect. Their disadvantage is the relatively high price. Liquid soaps are based on both K-salts of natural fatty acids and on synthetic anionic surfactants. In aqueous solution, they contain less detergent substances than solid soaps, have the customary additives, if appropriate with viscosity-regulating constituents and pearlescing additives. Because of their convenient and hygienic application from dispensers, they are preferably used in public washrooms and the like.

Detergent lotions for particularly sensitive skin are based on mild-acting synthetic surfactants with additives of skin-care substances, pH neutral or slightly acidic (pH 5, 5). To cleanse especially the facial skin, there are a number of other preparations, such as face lotions, cleansing lotions, milk, creams, pastes; Face packs serve z. T. the cleaning, but mainly the refreshment and care of the facial skin. Facial waters are mostly aqueous-alcoholic solutions with low surfactant levels and other skin-care substances. Cleansing lotions, - Milk, creams and pastes are usually based on O / W emulsions with relatively low levels of fat components with cleansing and nourishing additives. So-called Scruffing and exfoliating preparations contain mildly keratolytic substances for the removal of the upper dead skin-horn layers, eg. T. with additives of abrasive powders. Almond bran, which has long been used as a mild skin cleanser, is still a component of such preparations today. Anti-bacterial and anti-inflammatory agents are also included in cleansing skin cleansing products, as the sebum collections in comedones are a breeding ground for bacterial infections and tend to cause inflammation. The wide range of skin cleansing products on offer varies in composition and content Active ingredients tailored to the different skin types and to specific treatment goals.

The bath additives offered for skin cleansing in the bath or shower have been widely used. Bath salts and bath tablets are intended to soften, color and perfume the bath water and generally do not contain any washing-active substances. By softening the bath water, they promote the cleansing power of soaps, but are primarily intended to have a refreshing effect and enhance the bathing experience. Of greater importance are the bubble baths. With a higher content of moisturizing and skin-caring substances one speaks also of cream baths.

The skin care that follows the cleansing has two main goals: Firstly, it is supposed to restore the skin's uncontrolled ingredients such as horny cells, fatty lipids in the skin, acidifier and water to natural equilibrium, and secondly it should help the skin's natural aging process Possible damage caused by weather and environmental influences as far as possible counteract. Skin care and skin protection products are available in large numbers and in many forms of preparation. The most important are skin creams, lotions, oils and skin gels. The creams and lotions are based on emulsions in O / W (oil in water) or W / O (water in oil) form. The main components of the oil or. Fat or lipid phase are fatty alcohols, fatty acids, fatty acid esters, waxes, Vaseline, paraffins and other fat and oil components mainly of natural origin. In the aqueous phase, besides water, mainly moisturizing and moisture-retaining substances are contained as essential skin-care active substances, furthermore consistency-regulating or viscosity-regulating agents. Other additives, such as preservatives, antioxidants, complexing agents, perfume oils, colorants and special active substances, depending on their solubility and their stability. the properties of one of the two phases mentioned above. Essential for the emulsion type and its properties is the selection of the emulsifier system. Its selection can be made according to the HLB system. According to their application range, the creams or lotions can be divided into day creams and night creams. Day creams are usually designed as O / W emulsions, they quickly penetrate the skin, without leaving a greasy finish; one calls it therefore z. T. also as dry creams, matte creams or Vanishing- Creams. Night creams are mostly W / O emulsions, they are absorbed by the skin more slowly and often contain special active ingredients that are supposed to cause a regeneration of the skin during the night. Some of these preparations are also referred to as nutritional creams, although a diet of cell metabolism in the skin can only be done through the bloodstream; The term nutrient cream is therefore controversial. So-called cold creams are mixed emulsions of the O / W and W / O type, with the oil phase predominating in terms of quantity. In the classic Cold Cream was when applying the z. T. only unstable emulsified water released and produced by evaporation a cooling effect, which gave this preparation form its name.

The variety of special agents used in skin care products and their attributed effects can not be discussed in detail here. Mention should be made of milk protein products, egg yolks, lecithins, lipids, phosphatides, cereal germ oils, vitamins - in particular vitamin F and biotin, formerly known as skin vitamin (vitamin H), as well as hormone-free placenta extracts. Earlier hormones sometimes used are no longer used because they are classified as active pharmaceutical ingredients and should not be used in cosmetic products.

Skin oils are one of the oldest product forms of skin care and are still used today. It is based on non-drying vegetable oils such as almond oil or olive oil, with additions of natural vitamin oils such as wheat germ oil or avocado oil, as well as oily plant extracts of, for example, B. St. John's wort, chamomile u. ä.

The addition of antioxidants to rancidity is essential, desired fragrance notes are achieved by perfume oils, an addition of paraffin oil or liquid fatty acid esters is used to optimize the application properties.

Skin gels are semi-solid transparent products that are stabilized by appropriate gelling agents. A distinction is made between oleogel (anhydrous), hydrogels (oil-free) and oil / water gels. The type selection depends on the desired application purpose. The oil / water gels contain high levels of emulsifier and have certain advantages over emulsions in both aesthetics and application. Foot baths are said to have a good cleansing, refreshing, circulation-promoting and invigorating effect as well as deodorising and softening the cornea. Foot bath additives are available as bath salts and bubble baths. They exist z. Example of basic mixtures of sodium carbonate, sodium bicarbonate and sodium perborate or sodium hexametaphosphate, sodium sulfate, sodium perborate and 1% sodium lauryl sulfate as a foam component with antiperspirant, deodorant, optionally bactericidal and / or fungicidal additives and fragrances and dyes. Foot powders should be used after foot washing and / or interspersed with stockings and shoes, skin-smoothing, cooling, moisturizing, antiperspirant, antiseptic, deodorising and possibly softening the cornea. They usually consist of 85% talc with additions of silica powder, aluminum hydroxychloride, salicylic acid and optionally bactericides, fungicides, deodorants and fragrances. Foot creams or foot balms are used for skin care as well as for massaging the muscles of the foot and lower leg. Foot creams are usually O / W emulsions from z. B. 30% isopropyl myristate, 10% polysorbate, 4, 2% Ummetallmetahydroxid aluminum and 55, 8% water as the base formulation; Foot balms are mostly anhydrous and. contain z. 85% petroleum jelly, 5% paraffin, 3% lanolin, 3% methyl salicylate, 2% camphor, 1% menthol and 1% eucalyptus oil. Corneal remedies such. B. "Rubbelcremes" are rubbed on the skin until the cornea is abraded crumbly. A frame formulation consists of 25% paraffin, 2% stearic acid, 2% beeswax, 2% spermaceti, 2% glycerol monostearate, 0.5% 2, 2 ', 2 "-nitrilotriethanol, 1% perfume oil, 0.2% 4-hydroxybenzoic acid and 65% , 3% water.) Nail wrinkle tinctures are used to soften keratinization in the nail folds and to keep the nail edges soft on ingrown toenails, mainly on the big toes.

A frame formulation is made up of 10% 2, 2 ', 2 "-nitrilotriethanol, 15% urea, 0, 5% fatty alcohol polyglycol ether and 74.5% water Further cosmetic agents preferred according to the invention are agents for influencing the body odor, in particular deodorising agents Such deodorants can mask, remove or destroy odors, and unpleasant body odors are caused by bacterial decomposition of perspiration, especially in the moist warm armpits where microorganisms find good living conditions Accordingly, the most important ingredients of deodorants are germ-inhibiting substances However, preferred active ingredients have only a bacteriostatic effect and by no means completely kill the bacterial flora can all suitable preservatives are directed specifically against gram-positive bacteria. These are, for example, Irgasan DP 300 (trichloro, 2,4,4'-trichloro-2'-hydroxydiphenyl ether), chlorhexidine (1,1'-hexamethylenebis (5- (4'-chlorophenyl) -biguanide) and 3,4 , 4'-trichlorocarbanilide. Also quaternary ammonium compounds are also suitable in principle their high antimicrobial effectiveness, all these substances are preferably used only in low concentrations of about 0, 1 to 0, 3 wt .-%. Furthermore, numerous fragrances also have antimicrobial properties. Accordingly, such fragrances having antimicrobial properties are preferably used in deodorants. Particular mention may be made here of farnesol and phenoxyethanol. Therefore, it is particularly preferred if the deodorants according to the invention contain such self-bacteriostatically effective fragrances. The fragrances may preferably be in the form of fragrance alcohol alkoxylates. However, it is also possible that antibacterial fragrances are used together with fragrance alcohol alkoxylates and are thus present in mixtures with other fragrances. Another group of essential ingredients of deodorants are enzyme inhibitors which inhibit the decomposition of the sweat by enzymes, such as citric acid diethyl ester or zinc glycinate. Essential ingredients of deodorants are also antioxidants that are supposed to prevent oxidation of the sweat components.

In a further likewise preferred embodiment of the invention, the cosmetic agent is a hair setting agent which contains polymers for strengthening. It is particularly preferred if among the polymers at least one polyurethane is included.

The can. agents according to the invention in a preferred embodiment, water-soluble polymers from the group of nonionic, anionic, amphoteric and zwitterionic polymers.

Water-soluble polymers are to be understood as meaning those polymers which are more than 2.5% by weight soluble in water at room temperature.

Water-soluble polymers preferred according to the invention are nonionic. Examples of suitable nonionic polymers are: polyvinylpyrrolidones, for example those sold under the name Luviskol ^R (BASF). Polyvinylpyrrolidones are preferred nonionic polymers within the scope of the invention.

Vinylpyrrolidone-vinyl ester copolymers, for example as sold under the trade name Luviskol ^R (BASF). Luviskol ^R VA 64 and Luviskol® VA 73, each vinylpyrrolidone-vinyl acetate copolymers, are particularly preferred nonionic polymers.

Cellulose ethers, such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, as marketed, for example, under the trademarks Culminal ^R and Bencel ^R (AQUALON). Examples of suitable amphoteric polymers are the octyl acrylamide / methyl methacrylate available under the names Amomer ^R and Amphomer ^R LV-71 (DELFT NATIONAL). Butylaminoethyl methacrylate 2-hydroxypropyl methacrylate-copolymers.

Suitable zwitterionic polymers are, for example, the polymers disclosed in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL).

According to the invention suitable anionic polymers are u. a. :

Vinyl acetate crotonic acid copolymers such as, for example, under the names Resyn ^R (NATIONAL STARCH), Luviset ^R (BASF) and Gafset ^R (GAF) are commercially available. Vinylpyrrolidone-vinyl acrylate copolymers, available, for example, under the trademark Luviflex ^R (BASF). A preferred polymer is the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex ^R VBM-35 (BASF).

Acrylic acid / ethyl acrylate / N-tert. Butylacrylamide terpolymers sold in play, under the name Ultrahold strong ^R (BASF).

In cases where the polyurethane contains ionic groups, it has been found to be useful if other water-soluble polymers are non-ionic or of the same ionicity.

The hair treatment compositions according to the invention contain water-soluble polymers, depending on the type of hair treatment agent, which is not restricted, preferably in amounts of 0.01 to 20 wt .-%, in particular 0, 1 to 10% by weight, based on the total agent.

The polyurethanes and the water-soluble polymers are preferably present in a ratio of 1:10 to 10: 1 in the inventive compositions. A ratio of 2: 1 to 1: 1 has proven to be particularly suitable in many cases. The hair-setting corrugations according to the invention are in particular hair-setting agents, hair sprays and hair-drying waves. Hairsprays are a particularly preferred embodiment of the invention Haarfesttegemittet. The agents according to the invention can furthermore, in a likewise preferred embodiment, also be formulated as foam aerosol with the aid of a propellant.

The preparations according to the invention comprising one or more alkoxylated fragrance alcohols show an optimized fragrance impression due to the content of the alkoxylated fragrance alcohols. Thus, in preparations for which the alkoxylated fragrance alcohols prepared in the manner described in this application are distilled prior to addition to the preparation and thus freed from the fragrant fragrance alcohol (the alkoxylated fragrant alcohol was almost odorless before addition), the alkoxylated fragrance alcohols an already characterizing the preparation fragrance, which persists for a long time and thus survive a longer storage or transport time of the (optionally surfactant) preparation. The fragrance is also well transferred to the object to be treated and sticks there reliably; it is released over a longer period of time and thus leads reliably to the desired fragrance. This can be described as surprising both for detergents and cleaners and for cosmetic preparations.

In particular, fragrances are added to surfactant-containing preparations in order to improve the aesthetic overall impression of the products and to provide the consumer, in addition to the technical performance (washing, rinsing, cleaning result), a sensorically typical and unmistakable product. In a preferred embodiment of the present invention, in addition to the alkoxylated fragrance alcohols, it is possible to add to the surfactant-containing preparations one or more further components leaving an aroma impression. As perfume oils or perfumes, individual perfume compounds can be used, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons.

Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, cyclohexylsalicylate, benzylsalicylate, floramate, melusate and jasmacyclate. Also to be mentioned here are the esters of fragrance alcohols with inorganic acids or organic acids, as disclosed in the aforementioned prior art. Ethers include, for example, benzyl ethyl ether and ambroxan. The aldehydes include, for. B. linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal. The ketones include the ionones, alpha-isomethylionone, and methyl cedryl ketone.

The alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene.

Preference is given to using mixtures of different fragrances which are coordinated with one another in such a way that together they produce an attractive fragrance note.

Such perfume oils may also contain natural fragrance mixtures as are available from plant sources. As natural fragrances may be mentioned: extracts of flowers (lily, lavender, lime blossom, orange blossom, chamomile, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain, sage, lemon balm, mint, cinnamon leaves), Fruits (aniseed, coriander, caraway, nutmeg, cloves, juniper), fruit peel (bergamot, lemon, oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus, vetiver), wood (pine, sandalwood) , Guajac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, Olibanum, Opoponax, Labdanum). Furthermore, animal raw materials come into question, such as civet and Castoreum.

Usually, the content of fragrances in the range up to 2 wt .-% of the total preparation.

These can be incorporated directly into the detergent preparations; but it may also be advantageous to apply the fragrances on carriers that enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles. As such carrier materials, for example, cyclodextrins have been proven. The cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.

D3) Means for papermaking

Another field of application of farnesyl alkoxylates according to the invention is papermaking. In the fiber-containing mixtures used for this purpose (as a rule aqueous suspensions of fibrous materials, which may also partly originate from the waste paper spread), one or more of the inventive farnesyl alkoxylates are usually present in an amount of 0.001 to 5% by weight, such as, for example in a crowd from 0, 01 to 4 wt .-%, or in an amount of 0, 02 to 3 wt .-% or 0, 05 to 2 wt .-%, based on the total weight of the mass, or they are of the Papermaking added. An essential component of such pulp compositions is usually a chemical pulp, ie pulp, which has been obtained by chemical pulping of a lignocellulosic material such as wood. These include, for example, sulfate pulp, sulfite pulp and / or soda pulps, wherein the pulp may be unbleached or bleached. Among the bleached pulps, chlorine-bleached or, in particular, low-chlorine or chlorine-free pulps, such as ECF pulp and TCF pulp, are used. Preference is given to unbleached pulp. Also suitable is pulp from annual crops, such as pulp based on rice, wheat, sugar cane (bark), bamboo or kenaf. Typically, the level of chemical pulp in the pulp composition is in the range of 10 to 80 weight percent, often in the range of 20 to 70 weight percent, based on total pulp in the pulp composition. Partly this can also be replaced by other fibers, such as recycled paper pulp. Other fiber components include wood pulp, such as wood pulp (= mechanical pulp), z. For example, white ground or brown ground, thermomechanical pulp (TMP), chemo-thermomechanical pulp (CTMP), semi-pulp, high yield pulp, and refiner mechanical pulp (RMP).

In addition, other conventional additives can be used. Examples of customary additives are the additives customary in paper production for improving or modifying the paper properties, such as fillers, sizing agents, wet and dry strength agents, antiblocking agents, flame retardants, antistatic agents, water repellents, dyes and optical brighteners, and process chemicals, such as retention agents , Flocculants and dehydrating agents, fixatives, slimicides, wetting agents, defoamers, biocides and the like.

Examples of conventional wet strength agents are the polyamides commonly used for this purpose, epichlorohydrin resins, melamine-formaldehyde resins and cationic glyoxylated polyacrylamides. Examples of conventional dry strength agents are: native starches, starch derivatives, dextranes, cationized starch, cationically glyoxylated polyacrylamides, polyvinylamines, cationic, anionic or amphoteric polyacrylamides and mixtures thereof with inorganic dry strength agents. Examples of sizing agents (mass and surface sizing agents) are resin glues, casein and comparable proteins, starch, polymer dispersions, reactive sizing agents, in particular alkyldiketenes and alkylsuccinic anhydrides. In addition, it is also possible to add to the aqueous pulp suspension customary fillers, insofar as these are not already introduced by the waste paper pulp. Examples of suitable fillers are, in particular, calcium carbonate, such as chalk, kaolin, titanium dioxide, gypsum, precipitated calcium carbonate, talc, silicates.

Examples of typical retention aids are aluminum sulfate and polyaluminum chlorite. Microparticle systems of high molecular weight polyacrylamides and bentonite or colloidal silica can also be used as retention aids. As a retention agent can further combinations of microparticle systems of high molecular weight polyacrylamides and bentonite or colloidal silica with an anionic organic polymer, in particular anionic, optionally crosslinked polyacrylamides use. As retention agents based on microparticle systems of this type, it is known, for example, from EP 462365, WO 02/33171, WO 01/34908 or WO 01/34910. As a retention agent it is also possible to use partially hydrolyzed homopolymers of N-vinylformamide and partially hydrolyzed copolymers of N-vinylformamide with diallyldimethylammonium chloride, N, N-dimethylaminoethylacrylamide,

Use Ν, Ν-dimethylaminopropylacrylamide. Further retention aids are microparticle systems composed of high molecular weight polyvinylamines and anionic, cationic or amphoteric, crosslinked polyacrylamides, as are known, for example, from US 2003/0192664 A1.

Examples of customary flocculants and dehydrating agents are polyethyleneimines, polyamines having molar masses of more than 50,000, polyamidoamines, which may optionally be prepared by grafting with ethyleneimine and subsequent crosslinking with z. B. Polyethylenglykol- dichlorohydrin ethers or are crosslinked with epichlorohydrin, polyether amines, polyvinyl imidazoles, polyvinyl imidazolines, polyvinyl tetrahydropyridines, Polydialkylaminoalkylvinyl- ether, polydialkylaminoalkyl (meth) acrylates in protonated or quaternized form, polydiallyldialkylammonium halides, in particular polydiallyldimethylammonium.

Examples of conventional fixing agents are: aluminum sulfate, polyaluminum chlorites, as well as the customary for this purpose cationic polymers, eg. Cationic polyacrylamides, polyethyleneimines, polyvinylamines, polyimidazolines, polyimidazoles, polyamines, dicyandiamide resins, poly-DADMAC, Mannich products, and Hofmann products.

The type and amount of the process chemicals and the fillers depends in a manner known per se on the requirements of the paper machine and the desired type of paper.

The pulp suspension is dewatered in a paper machine to form paper or cardboard. If appropriate, it is possible, before introducing the pulp Dilute pension with water (so-called thin material). The addition of the process chemicals can be done both before dilution and after dilution. Subsequently, the pulp is dewatered in a conventional manner to form a sheet. The dewatering is typically carried out in a paper machine in which the usual steps of paper formation are performed, ie sheet forming in the wire section, densification to remove the bulk of water in the press section, drying in the dryer section, calendering smoothing and optionally supercalendering , Optionally, the dryer section may also comprise a size press in which the paper is treated with a low viscosity size liquor for surface hardening. Optionally, the paper machine may also comprise a coating unit in which the paper is coated with a coating color. An overview of the common processes for papermaking can be found in Roempp, Lexikon Chemie, 10th Edition, Thieme Verlag Stuttgart, 1998, pp. 31, 10 to 31, 15 and in Ulman's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM (R. -PAT, Paper and Pulp, Wiley-VCH 1997).

Typical paper types include:

Writing papers, ie filled and fully sized papers with smoothed surfaces, typically having a basis weight in the range of 30 to 80 g / m ² and a filler content in the range of 5 to 30% by weight and whose surfaces are usually painted ;

Printed papers, ie papers which are uncoated or coated and suitable for printing, which typically have a basis weight in the range from 40 to 150 g / m ² and have a filler content of up to 20% by weight; Newsprint papers, which typically have a basis weight in the range of 38 to 50 g / m ² and may have a filler content in the range of up to 18% by weight;

Packaging papers which typically have a basis weight in the range of 70 to 250 g / m ² and have a filler content of up to 15% by weight;

Cardboard or solid board, which typically have a basis weight in the range of 250 to 1000 g / m ² and may have a filler content of up to 15 wt .-%;

D4) fuel additives The aforementioned farnesyl alkoxylates according to the invention can also be used according to the invention as fuel additives individually or in admixture with other fuel additives (in the form of a so-called additive package). The fuel additized with the farnesyl alkoxylate according to the invention is a gasoline or a middle distillate fuel, especially a diesel fuel. In this case, the compounds of the invention are usually used in amounts of 0.00001 to 10 wt .-% or 0.0001 to 5 wt .-% or 0.001 to 2 wt .-% or 0.01 to 1 wt .-% based on the total weight of the additized fuel used.

The fuel may contain other conventional additives.

In the case of diesel fuels, these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocene, metal deactivators, Dyes and / or solvents.

In the case of gasoline fuels, these are mainly friction modifiers, corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.

Typical examples of suitable co-additives are listed in the following section:

(1) detergent additives

The usual detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical with a number-average molecular weight (M _n ) of from 85 to 20 000 and at least one polar group selected from:

(a) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;

(b) nitro groups, optionally in combination with hydroxyl groups;

(c) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;

(d) carboxyl groups or their alkali metal or alkaline earth metal salts; (e) sulfonic acid groups or their alkali metal or alkaline earth metal salts;

Polyoxy-C 2 to C 4 -alkylene groups terminated by hydroxyl groups, mono or polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;

Carbonsäureestergruppen;

(h) succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups; and or

(i) by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings. The hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel has a number average molecular weight (M _n ) of 85 to 20,000, preferably 1 13 to 10,000, more preferably 300 to 5,000, more preferably 300 up to 3,000, more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1,500. The typical hydrophobic hydrocarbon radicals are in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M _n of preferably from 300 to 5,000, particularly preferably from 300 to 3,000, more preferably from 500 to 2,500, even more preferably from 700 to 2,500 and in particular from 800 to 1,500.

As examples of the above groups of detergent additives, the following are mentioned:

Mono- or polyamino groups (a) containing additives are preferably polyalkylene mono- or Polyalkenpolyamine based on polypropene or of highly reactive (ie with predominantly terminal double bonds) or conventional (ie with predominantly central double bonds) polybutene or polyisobutene with M _n = 300 to 5000 , particularly preferably 500 to 2500 and in particular 700 to 2500. Such additives based on highly reactive polyisobutene, which from the polyisobutene, which may contain up to 20 wt .-% of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethyl-enpentamine, are known in particular from EP-A 244 616. If one starts with the preparation of the additives of polybutene or polyisobutene with predominantly intermediate double bonds (usually in the β and γ position), the preparation route by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl or Carboxyl compound and subsequent amination under reductive (hydrogenating) conditions to. For amination here amines, such as. As ammonia, monoamines or the above polyamines, are used. Corresponding additives based on polypropene are described in particular in WO-A 94/24231. Further special monoamino groups (a) containing additives are the hydrogenation products of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97/03946. Further special monoamino groups (a) containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262. Nitro groups (b), optionally in combination with hydroxyl groups, containing additives are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A96 / 03367 and in WO-A 96/03479 are described. As a rule, these reaction products are mixtures of pure nitropolyisobutenes (for example α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example α-nitro-β-hydroxypolyisobutene).

Hydroxyl groups in combination with mono- or polyamino groups (c) containing additives are in particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds having poly isobutene with M _n = 300 to 5000 with ammonia, mono- or polyamines, as described in particular in EP -A 476 485 are described.

Carboxyl groups or their alkali metal or alkaline earth metal salts (d) containing additives are preferably copolymers of C2 to C4o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remainder of the Carboxyl groups are reacted with alcohols or amines. Such additives are known in particular from EP-A 307 815. Such additives serve primarily to prevent valve seat wear and, as described in WO-A 87/01 126, can advantageously be used in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.

Sulfonic acid groups or their alkali metal or alkaline earth metal salts (e) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobern- steinsäurealkylesters, as described in particular in EP-A 639 632. Such additives are mainly used to prevent valve seat wear and can be used with advantage in combination with conventional fuel detergents such as poly (iso) butenines or polyetheramines.

Polyoxy-C2-C4-alkylene (f) containing additives are preferably lyether or polyetheramines, which by reaction of C2 to C6o-alkanols, C6 to C3o-alkanediols, mono- or D1-C2 to C3o-alkylamines, C 1 -C 30 -alkylcyclohexanols or C 1 -C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines are available. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. In the case of polyethers, such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, isononylphenol butoxylates and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Carboxylic ester groups (g) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm ² / s at 100 ° C, as described in particular in DE-A 38 38 918 are described. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also fulfill carrier oil properties.

Succinic anhydride-derived groupings containing hydroxyl and / or amino and / or amido and / or imido groups (h) containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenylsuccinic anhydride which by reaction of conventional or highly reactive polyisobutene with M _n = preferably 300 to 5000, more preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride on a thermal route in an En Reaction or via the chlorinated polyisobutene are available. The groupings having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with an acid and an amide function, carbonic acid imides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, still have free amine groups, or diimides which are formed by reacting di- or polyamines with two succinic acid derivatives. In the presence of imido groups (h), however, the further detergent additive according to the present invention is used only up to a maximum of 100% of the amount by weight of compounds having betaine structure. Such fuel additives are well known and described, for example, in documents (1) and (2). Preferably, it is the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines, and more preferably the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest here are reaction products with aliphatic polyamines (polyalkyleneimines), in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.

By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings (i) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenols may be derived from conventional or highly reactive polyisobutene having M _n = 300 to 5,000. Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.

One or more of said detergent additives may be added to the fuel in such an amount that the dosage rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm.

(2) carrier oils

Co-used carrier oils may be mineral or synthetic. Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil" known and obtained in the refining of mineral oil fraction (Vakuumdestillatschnitt with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.

Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternalolefins), (poly) esters, poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols. Examples of suitable polyolefins are olefin polymers having M _n = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated). Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 - to C 4 -alkylene groups, which are prepared by reacting C 2 - to C 6 -alkanols, C 6 - to C 3 -oxanediols, mono- or C 1 -to C 3 -alkylamines, Cr to C 30 -alkylcyclohexanols or C 1 to C 30 -alkylphenols having from 1 to 30 mol of ethylenoxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamines or Polyamines are available. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, P0IV-C2 to C6 alkylene oxide amines or functional derivatives thereof may be used as the polyether amines. Typical examples are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates, and the corresponding reaction products with ammonia.

Examples of carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B. di- (n- or isotridecyl) phthalate.

Further suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617.

Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C3 to C6 alkylene oxide units, for. For example, propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is, in particular, a straight-chain or branched C 6 - to C 18 -alkyl radical. Specific examples include tridecanol and nonylphenol. Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric C6- to Cis-aliphatic alcohols with C3- to C6-alkylene oxides. Examples of monohydric aliphatic C 6 -C 18 -alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, Tetradecanol, pentadecanol, hexadecanol, octadecanol and their constituent and positional isomers. The alcohols can be used both in the form of pure isomers and in the form of technical mixtures. A particularly preferred alcohol is tridecanol. Examples of C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1, 2-propylene oxide, butylene oxide, such as 1, 2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Among these, particularly preferred are C ₃ -C ₄ -alkylene oxides, ie, propylene oxide such as 1, 2-propylene oxide and butylene oxide such as 1, 2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Specifically, butylene oxide is used. Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.

Particular carrier oils are synthetic carrier oils, the alcohol-initiated polyethers described above being particularly preferred.

The carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight. (3) cold flow improver

Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility. In particular, the usually used for middle distillates of fossil origin, ie for conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI") come into consideration. However, it is also possible to use organic compounds which, when used in conventional diesel fuels, have in part or predominantly the properties of a wax anti-settling additive ("WASA"). Also, they can act partly or predominantly as nucleators. However, it is also possible to use mixtures of organic compounds which are active as MDFI and / or which act as WASA and / or as nucleators. Typically, the cold flow improver is selected from:

(K1) copolymers of a C ₂ -C 4 -olefin with at least one further ethylenically unsaturated monomer;

 (K2) comb polymers;

 (K3) polyoxyalkylenes;

(K4) polar nitrogen compounds;

 (K5) sulfocarboxylic acids or sulfonic acids or their derivatives; and

(K6) poly (meth) acrylic acid esters. Mixtures of different representatives from one of the respective classes (K1) to (K6) as well as mixtures of representatives from different classes (K1) to (K6) can be used.

Suitable C2 to C4o-olefin monomers for the copolymers of class (K1) are for example those having 2 to 20, in particular 2 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular having a carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally (a-olefins) and internally. However, preferred are α-olefins, more preferably α-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and especially ethylene.

In the copolymers of class (K1), the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic alkenyl esters, (meth) acrylic esters and further olefins.

If further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 - to C 4 -olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, suitable further olefins are, in particular, C 10 -C ₄ -olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used. Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with Cr to C 2 alkanols, in particular C 1 to C 1 alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert Butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof.

Suitable carboxylic alkenyl esters are, for example, C 2 - to C 6 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched. Preferred among these are the vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those whose branching is in the α-position to the carboxyl group, the α-carbon atom being particularly preferably tertiary, ie the carboxylic acid being a so-called neocarboxylic acid. Preferably, however, the hydrocarbon radical of the carboxylic acid is linear. Examples of suitable carboxylic alkenyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding prope nyl esters, with the vinyl esters being preferred. A particularly preferred carboxylic acid genyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA").

Particularly advantageous ethylene-vinyl acetate copolymers and their preparation are described in WO 99/29748.

Also suitable as copolymers of class (K1) are those which contain two or more different carboxylic acid alkenyl esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the carboxylic acid alkenyl ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form. Terpolymers of a C2 to C ₄ oa olefin, a C to C2o alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 to C ₄ alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms as copolymers of the class (K1). Such terpolymers are described in WO 2005/054314. A typical such terpolymer is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.

The at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight. %, based on the total copolymer, copolymerized. The majority by weight of the monomer units in the copolymers of class (K1) thus usually comes from the C2 to C ₄ o-based olefins.

The copolymers of class (K1) preferably have a number average molecular weight M _{n of} from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.

Typical comb polymers of component (K2) are, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an α-olefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol available with at least 10 carbon atoms. Other suitable comb polymers are copolymers of α-olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb polymers may also be polyfumarates or polymaleinates. In addition, homopolymers and copolymers of vinyl ethers are suitable comb polymers. Suitable as a component of class (K2) Comb polymers are, for example, those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", NA Plate and VP Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 1 17 to 253 (1974). "Mixtures of comb polymers are also suitable.

Polyoxyalkylenes suitable as a component of class (K3) are, for example, polyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one, preferably at least two, linear alkyl groups each having from 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5,000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and in US Pat. No. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of from 100 to 5,000. Polyoxyalkylene mono- and diesters of fatty acids containing from 10 to 30 carbon atoms, such as stearic acid or behenic acid, are also suitable.

Polar nitrogen compounds suitable as component of class (K4) may be both of ionic and nonionic nature and preferably have at least one, in particular at least two, substituents in the form of a tertiary nitrogen atom of general formula> NR ⁷ , where R ^{7 is} a to C4o hydrocarbon residue. The nitrogen substituents may also be quaternized, that is in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. Preferably, the amines contain at least one linear Cs to C4o-alkyl radical. Examples of suitable primary amines for the preparation of said polar nitrogen compounds are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues, suitable secondary amines for this purpose are, for example, dioctadecylamine and methylbehenylamine. Also suitable for this purpose are amine mixtures, in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic". Suitable acids for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted by long-chain hydrocarbon radicals. In particular, the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines. The basis of this implementation product lying at least one tertiary amino group-containing poly (C2 to C2o-carboxylic acids) preferably contain at least 3 carboxyl groups, especially 3 to 12, especially 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units. The carboxylic acid units are suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains. The component of class (K4) is preferably an oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) of general formula IIa or IIb having at least one tertiary amino group

HOOC. _DD OOH

 B B

HOOC. .NU _D OOH

 B A B (IIa)

in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III

HOOC ' ^{B 1} N ^{' CH 2 'CH 2'}

 i

CH ₂ -CH ₂ -

(III) and the variable B denotes a C to Cig alkylene group. The compounds of the general formula IIa and IIb have in particular the properties of a WASA.

Furthermore, the preferred oil-soluble reaction product of component (K4), in particular that of general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are converted into amide groups.

Straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are, for example, 1, 1-ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-butylene, 1, 4-butylene ethylene, 2-methyl-1, 3-propylene, 1, 5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene pylene, 1, 6-hexylene (hexamethylene) and in particular 1, 2-ethylene. The variable A preferably comprises 2 to 4, in particular 2 or 3, carbon atoms.

C 1 - to C 18 -alkylene groups of variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and in particular methylene. Preferably, the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms.

The primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines may be selected from a variety of amines bearing hydrocarbon radicals, optionally linked together.

Most of these amines which are the oil-soluble reaction products of component (K4) are secondary amines and have the general formula HN (R ⁸ ) 2 in which the two variables R ⁸ independently of one another each represent straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular Cu - to C24-alkyl radicals mean. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the abovementioned secondary amines are derived with regard to their longer-chain alkyl radicals from naturally occurring fatty acid or from its derivatives. Preferably, the two radicals R ^{8 are the} same.

The abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present. Preferably, the oil-soluble reaction products of component (K4) are completely in the form of the amide structures.

Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or, in particular, Ditaigfettamin. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated dithiol fatty amine. Further typical examples of component (K4) are the N, N-dialkylammonium salts of 2-N ', Ν'-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of diethfamine, the latter being hydrogenated or can not be hydrogenated, and the reaction product of 1 mol of a Alkenylspirobislac- tons with 2 moles of a dialkylamine, for example Ditalgfettamin and / or tallow fatty amine, the latter two may be hydrogenated or unhydrogenated, called. Further typical structural types for the component of the class (K4) are cyclic compounds having tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/181 15. Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of the component of the class (K5) are, for example, the oil-soluble carboxylic acid amides and carboxylic esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in EP -A 261 957.

As cold flow improvers of the component of the class (K6) suitable poly (meth) acrylic esters are both homo- and copolymers of acrylic and methacrylic esters. Preference is given to copolymers of at least two different (meth) acrylic acid esters, which differ with respect to the fused-in alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight-average molecular weight of the polymer is preferably 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C14 and Cis alcohols wherein the acid groups are neutralized with hydrogenated tallamine. Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.

The middle distillate fuel or diesel fuel is the cold flow improver or the mixture of various cold flow improvers in a total amount of preferably 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 50 to 1000 wt. ppm and in particular from 100 to 700 ppm by weight, eg from 200 to 500 ppm by weight, added.

(4) Lubricity improver

Suitable lubricity improvers (or friction modifiers) are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described, for example, in WO 98/004656, and glycerol monooleate. The reaction products of natural or synthetic oils, for example triglycerides, and alkanolamines described in US Pat. No. 6,743,266 B2 are also suitable as such lubricity improvers. (5) corrosion inhibitors

Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation).

(6) Demulsifiers Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or polysiloxanes.

(7) Dehazer Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite) products available under the tradename.

(8) antifoam

Suitable antifoams are e.g. Polyether-modified polysiloxanes such as the TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename. (9) Cetane number improver

Suitable cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide. (10) Antioxidants

Suitable antioxidants are e.g. substituted phenols such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.

(1 1) Metal deactivators Suitable metal deactivators include salicylic acid derivatives such as N, N'-disalicylidene-1, 2-propanediamine.

(12) solvent

Suitable ones are e.g. non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example, toluene, xylenes, "white spirit" and products marketed under the trade names SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (Exxon Mobil), as well as polar organic solvents, for example Alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents usually go into the diesel fuel together with the abovementioned additives and co-additives, which they are intended to dissolve or dilute for better handling.

D5) solubilizing agent

The aforementioned farnesyl alkoxylates according to the invention can also be used according to the invention as solubilizers for aqueous systems in order to solubilize water-insoluble substances therein.

In this case, the compounds according to the invention are usually used in amounts of 0.01 to 50 wt .-% or 0.1 to 10 wt .-% or 1 to 8 wt .-% based on the total weight of the solubilized mixture. Optionally, additional surface-active additives such as e.g. be selected from among the surfactants described above.

D6) Agrochemical Compositions The compounds of the formula I according to the invention are furthermore suitable for use as adjuvants in agrochemical compositions or crop protection formulations, e.g. in herbicidal, fungicidal or insecticidal compositions.

The compounds I can be converted into the types customary for agrochemical compositions, e.g. As solutions, emulsions, suspensions, dusts, powders, pastes and granules. The composition type depends on the respective purpose.

The compositions generally contain 0.01 to 20 wt .-%, 0.1 to 10 wt .-% or 1 to 5 wt .-% of the compounds I.

The agrochemical compositions are prepared in a known manner (s. z. No. 3,060,084, EP-A 707,445 (for liquid concentrates), Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th ed., McGraw-Hill, New York, 1963, 8-57 and et seq., WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701, US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (John Wiley & Sons, New York, 1961), Hance et al .: Weed Control Handbook (8th Ed., Blackwell Scientific Publications, Oxford, 1989) and Mollet, H. and Grubemann, A .: Formulation technology (Wiley VCH Verlag, Weinheim, 2001). In addition to the active ingredient or the active ingredients and the compounds of the formula I according to the invention, the agrochemical compositions may also contain other adjuvants which are customary for crop protection agents, the choice of auxiliaries being based on the specific application form or the active ingredient. Examples of suitable auxiliaries are solvents, solid carriers, surface-active substances (such as further solubilizers, protective colloids, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if appropriate dyes and adhesives (for example for seed treatment).

Suitable solvents include water, organic solvents such as medium to high boiling point mineral oil fractions such as kerosene and diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, gycols, ketones such as cyclohexanone, gamma-butyrolactone, dimethyl fatty acid amides, fatty acids and fatty acid esters, and strong polar solvents, e.g. Amines such as N-methylpyrrolidone, into consideration. In principle, solvent mixtures and mixtures of the abovementioned solvents and water can also be used.

Solid carriers are mineral soils such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

As surface-active substances other than compounds of the formula I (adjuvants, wetting agents, adhesives, dispersants or emulsifiers), the alkali metal, alkaline earth metal, ammonium salts of aromatic sulfonic acids, eg. B. of lignin (Borresperse ^® grades, Borregaard, Norway), phenol, naphthalene (Morwet ^® types, Akzo Nobel, USA) and dibutyl (nekal ^® types, BASF, Germany), as well as fatty acid ren, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde , Polyoxyethylene octylphenol ethers, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ethers, alkylarylpolyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulphite liquors and proteins, denatured proteins, polysaccharides (eg methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol ^® types, Clariant, Switzerland), polycarboxylates (Sokalan ^® types, BASF, Germany), polyalkoxylates, polyvinylamine (Lupamin ^® grades, BASF, Deuts chland), polyethylene imine (Lupasol ^® types, BASF, Germany), polyvinylpyrrolidone and copolymers thereof.

Examples of thickeners (ie, compounds that give the composition a modified flow properties, ie high viscosity at rest and low viscosity in motion) are polysaccharides and organic and inorganic sheet minerals, such as xanthan gum (Kelzan ^®, CP Kelco, U.S.A.), Rhodopol ^® 23 (Rho dia, France) or Veegum ^® (RT Vanderbilt, USA) or attaclay ^® (Engelhard Corp., NJ, USA).

Bactericides may be added to stabilize the composition. Examples of bactericides are those based on diclorophene and Benzylalkoholhemi- formal (Proxel ^® Fa. ICI or Acticide ^® RS Fa. Thor Chemie and Kathon ^® MK Fa. Rohm & Haas) and Isothiazolinonderivaten as Alkylisothiazolinonen and Benzisothiazolinonen (Acticide ^® MBS of Fa. Thor Chemie).

Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.

Examples of defoamers are silicone emulsions (such as, for example, silicone ^® SRE, Wacker, Germany or Rhodorsil ^®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.

Examples of colorants are both water-insoluble pigments and water-soluble dyes. Examples which may be mentioned are those under the designations Rhodamine B, CI Pigment Red 1 12 and CI Solvent Red 1, Pigment blue 15: 4, Pigment blue 15: 3, Pigment blue 15: 2, Pigment blue 15: 1, Pigment blue 80, Pigment yellow 1, Pigment yellow 13, Pigment red 48: 2, Pigment red 48: 1, Pigment red 57: 1, Pigment red 53: 1, Pigment orange 43, Pigment orange 34, Pigment orange 5, Pigment green 36, Pigment green 7, Pigment white 6, Pigment brown 25, Basic violet 10, Basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108 known dyes and pigments.

Examples of adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and cellulose ethers (Tylose ^®, Shin-Etsu, Japan).

For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration. Powders, litter and dusts can be prepared by mixing or joint grinding of the compounds I and, if present, other active ingredients with at least one solid carrier.

Granules, for. As coated, impregnated and homogeneous granules can be prepared by binding the active ingredients to at least one solid carrier. Solid carriers are z. As mineral earths, such as silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, bark, wood and nutshell flour, cellulose powder and other solid carriers.

Oils of various types, wetting agents, adjuvants, herbicides, bactericides, other fungicides and / or pesticides may also be added to the active substances or the compositions containing them, if appropriate also immediately before use (tank mix). These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1. As adjuvants in this sense are in particular: organically modified polysiloxanes, eg. B. Break Thru S ^240® ; Alcohol alkoxylates, eg. B. Atplus 245 ^®, Atplus MBA ^® 1303 Plurafac ^® LF 300 and Lutensol ON 30 ^®; EO-PO block polymers, eg. B. Pluronic RPE 2035 ^® and Genapol B ^®; Alcohol ethoxylates, eg. B. Lutensol ^® XP 80; and sodium dioctylsulfosuccinate, e.g. B. Leophen ^® RA.

The compositions according to the invention may contain one or more active substances selected from among herbicides, insecticides, growth regulators, fungicides. th.

The following nonlimiting list mentions active substances with which the compounds according to the invention can be used together,

A) strobilurins:

 Azoxystrobin, Dimoxystrobin, Coumoxystrobin, Coumethoxystrobin, Enestroburin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Pyrametostrobin, Pyraoxystrobin, Pyribencarb, Trifloxystrobin, 2- [2- (2,5-Dimethylphenyl-oxymethyl) phenyl] Methyl 3-methoxyacrylate, 2- (2- (3- (2,6-dichlorophenyl) -1-methyl-allylideneaminooxymethyl) -phenyl) -2-methoxyimino-N-methyl-acetamide;

B) Carboxylic acid amides:

- carboxylic acid anilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboin, fenfuram, fenhexamide, flutolanil, fluxapyroxad, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, Oxadixyl, oxycarboxine, penflufen, penthiopyrad, sedaxanes, tecloftalam, thifluzamide, tiaminil, 2-amino-4-methyl-thiazole-5-carboxanilide, N- (4'-trifluoromethylthiobiphenyl-2-yl) -3-difluoromethyl-1 -methyl-1H-pyrazole-4-carboxamide, N- (2- (1,3,3-trimethyl-butyl) -phenyl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide ;

 - Carboxylic acid morpholides: dimethomorph, flumorph, pyrimorph;

 Benzoic acid amides: flumetover, fluopicolide, fluopyram, zoxamide;

 Other carboxamides: carpropamide, diclocymet, mandipropamide, oxytetracycline, silthiofam, N- (6-methoxypyridin-3-yl) cyclopropanecarboxamide;

C) Azoles:

 - Triazoles: azaconazole, bitertanol, bromiconazole, cyproconazole, difenoconazole, diconoconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole , Simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole;

- imidazoles: cyazofamide, imazalil, imazalil sulfate, pefurazoate, prochloraz, triflumizole;

Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;

- Other: ethaboxam, etridiazole, hymexazole, 2- (4-chloro-phenyl) -N- [4- (3,4-dimethoxyphenyl) -isoxazol-5-yl] -2-prop-2-ynyloxy-acetamide ;

D) Nitrogen-containing heterocyclyl compounds

 Pyridines: fluazinam, pyrifenox, 3- [5- (4-chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine, 3- [5- (4-methyl-phenyl) -2, 3-dimethyl-isoxazolidin-3-yl] -pyridine;

Pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepanipyrim, Nitrapyrin, nuarimol, pyrimethanil;

 - piperazines: triforins;

 - Pyrroles: fludioxonil, fenpiclonil;

 - morpholines: aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph; - piperidines: fenpropidine;

 Dicarboximides: fluorimide, iprodione, procymidone, vinclozolin;

 non-aromatic 5-membered heterocycles: famoxadone, fenamidone, flutianil, octhilinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydropyrazole-1-thiocarboxylic acid allyl ester;

- Other: acibenzolar-S-methyl, amisulbrom, anilazine, blasticidin-S, captafol, captan, quinomethionate, dazomet, debacarb, diclomethine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, folpet, oxolinic acid, piperaline, proquinazid, pyroquilon, qui - Noxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propyl-chromen-4-one, 5-chloro-1 - (4,6-dimethoxypyrimidin-2-yl) -2-methyl-1 H-benzoimidazole, 5-chloro-7- (4-methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a ] pyrimidine, 5-ethyl-6-octyl- [1,2,4] triazolo [1,5-a] pyrimidin-7-ylamine;

E) carbamates and dithiocarbamates

 Thio and dithiocarbamates: Ferbam, Mancozeb, Maneb, Metam, Methasulphocarb, Metiram, Propineb, Thiram, Zineb, Ziram;

 Carbamates: Diethofencarb, Benthiavalicarb, Iprovalicarb, Propamocarb, Propamocarb hydrochloride, Valiphenal, N- (1- (1- (4-cyanophenyl) ethanesulfonyl) -but-2-yl) carbamic acid- (4-fluorophenyl) ester; F) Other fungicides

 Guanidines: dodine, dodine free base, guazatine, guazatine acetate, iminoctadine, iminoctadine triacetate, iminoctadin tris (albesilat);

 - antibiotics: kasugamycin, kasugamycin hydrochloride hydrate, polyoxines, streptomycin, validamycin A;

Nitrophenyl derivatives: binapacryl, diclorane, dinobutone, dinocap, nitrothal-isopropyl, tecnazene;

 Organometallics: fentin salts such as fentin acetate, fentin chloride, fentin hydroxide;

 Sulfur-containing heterocyclyl compounds: dithianone, isoprothiolanes;

Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;

 Organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophene, flusulphamide, hexachlorobenzene, pencycuron, pentachlorophenol and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanid, N- (4-chloro-2-nitro-phenyl) -N-ethyl-4- methyl-benzenesulfonamide;

Inorganic active substances: phosphorous acid and its salts, Bordeaux broth, copper salts such as copper acetate, copper hydroxide, copper oxychloride, basic beautiful copper sulphate, sulfur;

- Biological fungicide, plant strengtheners: Ampelomyces quis- qualis (. Eg the product AQ 10 ^® from Intrachem Bio GmbH & Co. KG, Germany), Aspergillus flavus (. Eg the product AFLAGUARD ^® from Syngenta, Switzerland), Aureobasidium pullulans ( eg the product BOTECTOR ^® from. bio-ferm GmbH, Germany), Bacillus pumilius (eg strain NRRL no. B-21661 in the products RHAPSODY ^®, SERENADE ^® MAX ^® and SERENADE ASO Fa. AgraQuest Inc., USA) Bacillus subtilis var. amyloliquefaciens FZB24 (eg the product TAEGRO ^® from. Novozyme Biologicals, Inc., USA), Candida oleophila I-82 (for example, the product ASPIRE ^® from. Ecogen Inc., USA), Candida saitoana (eg products BIOCURE ^® (mixed with lysozyme) and BIOCOAT ^® of Micro Flo Company, Company, USA (BASF SE) and Arysta) chitosan (eg ARMOR ZEN Fa. Botri- Zen Ltd., New Zealand), Clonostachys rosea f. catenulata, also called Gliocladium catenulatum: (. eg the product Contans ^® from Prophyta, Germany) (eg strain J1446. PresTop ^® from Verdera, Finland), Coniothyri- to minitans Crypho- Nectria parasitica (eg the product Endothia parasitica the company CNICM, France), Cryptococcus albidus (eg the product YIELD PLUS ^® Natural Plant. Fa. Anchor bio- Technologies, South Africa), Fusarium oxysporum (eg the products biofox ^® from. Siapa, Italy, and FUSACLEAN ^® from Protection, France), Metschnikowia fructicola (eg the product Shemer ^®, Fa.. AgroGreen, Israel), Microdochium dimerum (eg the product ANTI BOT ^® from Agrauxine, France), Phlebiopsis gigantea (eg the product ROTSOP ^® from . Verdera, Finland), Pseudozyma flocculosa (eg the product SPORODEX ^® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (eg. the product POLYVERSUM ^® from. Remeslo SSRO, Biopreparaty, Czech Republic), Reynoutria sachlinensis (eg the product RE GALIA ^® from Marrone BioInnovations, USA), Talaromyces flavus V1 17b (eg the product protus ^® from Kumiai Chemical Industry Co Fa. Prophyta, Germany), trichomes derma asperellum SKT-1 (eg, the product ECO-HOPE ^® from. ., Ltd., Japan), T. atroviride LC52 (eg the product SENTINEL ^® from. Agrimm Technologies Ltd, New Zealand), T. harzianum T-22 (eg the product PLANT SHIELD ^® from BioWorks Inc., USA), T . harzianum TH 35 (eg the product ROOT PRO ^® from MyControl Ltd., Israel), T. harzianum T-39 (for example, the products TRICHODEX ^® and TRICHODERMA 2000 ^® from. MyControl Ltd., Israel and Makhteshim Ltd., Israel ), T. harzianum and T. viride (eg the product TRICHOPEL the company Agrimm Technologies Ltd, New Zealand), T. harzianum and T. viride ICC012 ICC080 (eg the product remédier ^® WP Fa. Isagro Ricerca, Italy), T. po- lysporum and T. harzianum (eg the product Binab ^® from. Binab Bio-innovation AB, Sweden), T. stromaticum (eg the product TRICOVAB ^® from Ceplac, Bras ily), T. virens GL-21 (eg the product SOILGARD ^® from Certis LLC, USA), T. viride (eg the products TRIECO ^® from Ecosense Labs. (India) Pvt. Ltd., India and BIO-CURE ^® F from. T. Stanes & Co. Ltd., India), T. viride TV (eg the product T. viride TV1 company Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (eg the product BOTRY ZEN ^® of Botry-Zen Ltd Company, New Zealand);

 - Other: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamine, metrafenone, pyriofenone, mildiomycin, oxine-copper, prohexadione-calcium, spiroxamine, tolylfluanide, N- (cyclopropylmethoxyimino- (6-difluoromethoxy-2,3-difluorophenyl ) -methyl) -2-phenylacetamide, N '- (4- (4-chloro-3-trifluoromethyl-phenoxy) -2,5-dimethylphenyl) -N-ethyl-N-methylformamidine, N' - (4- (4-Fluoro-3-trifluoromethylphenoxy) -2,5-dimethylphenyl) -N-ethyl-N-methylformamidine, N '- (2-methyl-5-trifluoromethyl-4- (3-trimethylsilanyl) propoxy) -phenyl) -N-ethyl-N-methylformamidine, N '- (5-difluoromethyl-2-methyl-4- (3-trimethylsilanyl-propoxy) -phenyl) -N-ethyl-N-methylformamidine, 2- { 1 - [2- (5-Methyl-3-trifluoromethyl-pyrazol-1-yl) -acetyl] -piperidin-4-yl} -thiazole-4-carboxylic acid-methyl-

(1,2,3,4-tetrahydronaphthalen-1-yl) -amide, 2- {1- [2- (5-methyl-3-trifluoromethyl-pyrazol-1-yl) -acetyl] -piperidin-4-yl } -thiazole-4-carboxylic acid-methyl- (R) -1, 2,3,4-tetrahydronaphthalene-1-yl-amide, acetic acid-6-tert-butyl-8-fluoro-2,3-dimethyl-quinoline -4-yl-ester, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl-ester, A / -methyl-2- {1 - [2- (2- 5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl) -acetyl] -piperidin-4-yl} -A / - [(1R) -1, 2,3,4-tetrahydronaphthalene-1-yl ] -4-thiazolecarboxamide;

G) growth regulator

 Abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butraline, chlormequat (chlorequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipine, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfid , indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), metconazole, naphthalene acetic acid, N-6-benzyladenine, paclobutrazole, prohexadione (prohexadione-calcium), Prohydrojasmon, thidiazuron, tri-penthenol, tributylphosphorotrithioate, 2,3,5 tri-iodobenzoic acid, trinexapac-ethyl and uniconazole;

H) herbicides

 Acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamide,

Pretilachlor, propachlor, thenylchloride;

 Amino acid analogues: bilanafos, glyphosate, glufosinate, sulfosate;

 Aryloxyphenoxypropionates: clodinafop, cyhalofopbutyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;

Bipyridyls: diquat, paraquat;

 Carbamates and thiocarbamates: asulam, butylates, carbamides, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinates, orbencarb, phenmedipham, prochlorocarb, pyributicarb, thiobencarb, triallates;

 - cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim;

- Dinitroanilines: Benfluralin, Ethalfluralin, Oryzalin, Pendimethalin, Prodiamine, Trifluralin; Diphenyl ether: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen;

 Hydroxybenzonitriles: bromoxynil, dichlobenil, loxynil;

 Imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr;

 Phenoxyacetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, mecoprop;

 - Pyrazines: Chloridazon, Flufenpyr-ethyl, Fluthiacet, Norflurazon, Pyridate;

 - pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, pilinoram, picolinafen, thiazopyr;

 Sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, lodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosul furon, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1 - ((2-chloro-6-propylimidazo [1,2-b] pyridazin-3-yl) sulfonyl ) -3- (4,6-dimethoxypyrimidin-2-yl) urea;

 Triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozine, hexazinone, metachronon, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam;

 Ureas: chlorotoluron, da- muron, diuron, fluometuron, isoproturon, linuron, methabenzthiazuron, tebuthiuron;

 - other inhibitors of acetolactate synthase: bispyribac sodium, cloransulam methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, orthosulphamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxime, pyriftalid, pyriminobac-methyl, pyrimisulphane, pyrithiobac, pyroxasulphone, pyroxsulam;

- Other: Amicarbazone, Aminotriazole, Anilofos, Beflubutamide, Benazoline, Bencarbazone, Benfluresat, Benzofenap, Bentazone, Benzobicyclone, Bromacil, Bromobutide, Butafenacil, Butamifos, Cafenstrole, Carfentrazone, Cinidone-Ethlyl, Chlorthal, Cinnamethyl, Clomazone, Cumyluron , Cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechsler's monoceras, endothal, ethofumesate, etobenzanide, fentrazamide, flumigorac-pentyl, flumioxazin, flupoxam, fluorochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, Quinmerac, mesotrione, methylarsenoic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefon, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotol, pyrazoxyfen, pyrazolynate, quinoclamin, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-3- [2- (2-methoxy-ethoxymethyl) -6-trifluoromethyl-pyridine-3-carbonyl] -bicyclo [3.2.1] oct-3-en-2-one,

(3- [2-Chloro-4-fluoro-5- (3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl) -phenoxy] -pyridine-2 -yloxy) -acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -pyridazin-4-ol, 4- amino-3-chloro-6- (4-chloro-phenyl) -5-fluoro-pyridine-2-carboxylic acid, 4-Amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxy-phenyl) -pyridine-2-carboxylic acid methyl ester and 4-amino-3-chloro-6- (4-chloro-3 -dimethylamino-2-fluoro-phenyl) -pyridine-2-carboxylic acid methyl ester; I) insecticides

 Organo (thio) phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulphoton, ethion, fenitrothion, fenthione, isoxathione, malathion, methamidophosphate, methidathion , Methyl parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidone, phorates, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorinophos, terbufos, triazophos, trichlorfon;

 Carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamates;

 - pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin,

Insect growth inhibitors: a) chitin synthesis inhibitors: benzoylureas: chlorofluorazuron, cyramazine, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; Buprofezin, diophenolane, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) Juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spinotetramat;

 Nicotine receptor agonists / antagonists: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1- (2-chlorothiazol-5-ylmethyl) -2-nitrimino-3,5-dimethyl- [1, 3,5] triazinane;

 - GABA antagonists: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1 - (2,6-dichloro-4-methyl-phenyl) -4-sulfinamoyl-1H-pyrazole-3-thiocarbon acid amide;

 Macrocyclic lactones: Abamectin, Emamectin, Milbemectin, Lepimectin, Spinosid, Spinetoram;

 - mitochondrial electron transport chain inhibitor (METI) I acaricides: Fenazaquin, Pyridaben, Tebufenpyrad, Tolfenpyrad, Flufenerim;

 - METI II and III substances: Acequinocyl, Fluacyprim, Hydramethylnon;

 - decoupler: chlorfenapyr;

- inhibitors of oxidative phosphorylation: cyhexatin, diafenthiuron, fenbutatin oxide, propargite;

Inhibitors of the sloughing of insects: Cryomazine; Inhibitors of mixed function oxidases: piperonyl butoxide;

 Sodium channel blocker: indoxacarb, metaflumizone;

 - Other: Benclothiaz, Bifenazate, Cartap, Flonicamid, Pyridalyl, Pymetrozine, Sulfur, Thiocyclam, Flubendiamid, Chlorantraniliprole, Cyazypyr (HGW86); Cynopyphron, Flupyrazofos, Cyflumetofen, Amidoflumet, Imicyafos, Bistrifluron and Pyrifluquinazone.

The means are e.g. for controlling a variety of pathogens on various crops such as cereals, e.g. Wheat, rye, barley, triticale, oats or rice; Beets, z. Sugar or fodder beets; Kernel, stone and berry fruits, z. Apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; Legumes, z. Beans, lentils, peas, alfalfa or soybeans; Oil plants, e.g. Rapeseed, mustard, olives, sunflowers, coconut, cocoa, castor beans, oil palm, peanuts or soya; Cucurbits, z. Pumpkins, cucumbers or melons; Fiber plants, z. Cotton, flax, hemp or jute; Citrus fruits, z. Oranges, lemons, grapefruit or mandarins; Vegetables, z. Spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, squash or paprika; Laurel family, z. Avocados, cinnamon or camphor; Energy and raw material plants, eg. Corn, soy, wheat, rapeseed, sugarcane or oil palm; Corn; Tobacco; Nuts; Coffee; Tea; bananas; Wine (table and grapes); Hop; Grass, z. B. lawn; Sweet herb (Stevia rebaudaniä); Rubber plants; Ornamental and forest plants, z. As flowers, shrubs, deciduous and coniferous trees and on the propagation material, for. B. seeds, and the crop of these plants. The compositions of the invention are also suitable for controlling harmful fungi in the storage protection (also of crops) and in the protection of materials and buildings. The term "material and building protection" covers the protection of technical and non-living materials such. As adhesives, glues, wood, paper and cardboard, textiles, leather, color dispersions, plastics, coolants, fibers and tissues, against infestation and destruction by unwanted microorganisms such as fungi and bacteria. In particular, the following harmful fungi are considered in the wood and material protection: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.

Experimental part A) Materials and Methods

The chemicals used are unless otherwise specified commercially available products.

Hydrogenated farnesol can be prepared in a manner known per se. For example, can be used for the preparation of hexahydrofarnesol Raney-Ni (1 wt.% Based on farnesol), under the following conditions: Farnesol: ethanol 2: 1 (mass ratio), 100 ° C, 70 bar, 15 h. The degree of hydrogenation can be adjusted by adjusting the molar ratio of farnesol to hydrogen that has been compressed.

B) Production Examples Production Example 1: Preparation of hexahydrofarnesol-3 EO

In a stirred reactor, 327.1 g of hexahydrofarnesol (CAS No. 6750-34-1) and 1.26 g of a 44% aqueous KOH solution were initially charged. The mixture was dehydrated at 120 ° C and 20mbar for 30 minutes. Subsequently, it was made inert with nitrogen to a pressure of 0.5 bar. At a temperature of 160 ° C and a maximum pressure of 2.3 bar 189.5 g of ethylene oxide were metered. After dosing, the reactor contents cooled to 60 ° C. were neutralized by adding 0.66 g of acetic acid and the reactor was emptied. analytics

 OH = 151 mg KOH / g

pH (5% aqueous solution): 5.6

 Cloud point (method E according to DIN EN 1890): 43.7 ° C. Production example 2: Preparation of hexahydrofarnesol-5 EO

In a stirred reactor, 263.2 g of hexahydrofarnesol and 1, 26 g of a 44% aqueous KOH solution were presented. The mixture was dehydrated at 120 ° C and 20mbar for 30 minutes. Subsequently, it was made inert with nitrogen to a pressure of 0.5 bar. At a temperature of 160 ° C and a maximum pressure of 2.6 bar, 254.4 g of ethylene oxide were metered. After dosing the cooled to 60 ° C reactor contents was neutralized by the addition of 0.64 g of acetic acid and the reactor emptied. analytics

OH = 121.2 mg KOH / g pH (5% aqueous solution): 5.6

 Cloud point (method E according to DIN EN 1890): 64.9 ° C

Production Example 3: Preparation of hexahydrofarnesol-7 EO

220 g of hexahydrofarnesol and 1.32 g of a 44% strength aqueous KOH solution were placed in a stirred reactor. The mixture was dehydrated at 120 ° C and 20mbar for 30 minutes. Subsequently, it was made inert with nitrogen to a pressure of 0.5 bar. At a temperature of 160 ° C and a maximum pressure of 2.8 bar 297.6 g of ethylene oxide were metered. After dosing, the reactor contents cooled to 60 ° C. were neutralized by adding 0.63 g of acetic acid and the reactor was emptied.

analytics

 OH = 99.1 mg KOH / g

pH (5% aqueous solution): 6.0

 Cloud point (method E according to DIN EN 1890): 76.2 ° C

Preparation Example 4 Preparation of Hexahydrofarnesol 10 EO 175.6 g of hexahydrofarnesol and 1.25 g of a 44% strength aqueous KOH solution were initially introduced into a stirred reactor. The mixture was dehydrated at 120 ° C and 20mbar for 30 minutes. Subsequently, it was made inert with nitrogen to a pressure of 0.5 bar. At a temperature of 160 ° C and a maximum pressure of 3.0 bar 339.2 g of ethylene oxide were metered. After dosing, the reactor contents cooled to 60 ° C. were neutralized by adding 0.66 g of acetic acid and the reactor was emptied.

analytics

 OH = 80.9 mg KOH / g

pH (5% aqueous solution): 5.8

 Cloud point (method E according to DIN EN 1890): 84.7 ° C

Production Example 5 Preparation of Hexahydrofarnesol-5.4 EO-: 199 g of hexahydrofarnesol and 2.64 g of a 44% strength aqueous KOH solution were introduced into a stirred reactor. The mixture dehydrated at 120 ° C and 20mbar for 30 minutes. Subsequently, it was made inert with nitrogen to a pressure of 0.5 bar. At a temperature of 150 ° C and a maximum pressure of 2.3 bar 206.9 g of ethylene oxide were metered. After a reaction time of 15 minutes at 150 ° C., 101.1 g of propylene oxide were metered in at a temperature of 128 ° C. and a maximum pressure of 2.9 bar. After a post-reaction time of 2.5 hours at 128 ° C The reactor contents cooled to 60 ° C. were neutralized by adding 1.26 g of acetic acid and the reactor was emptied.

analytics

OH = 94.7 mg KOH / g

pH (5% aqueous solution): 6.4

 Cloud point (method E according to DIN EN 1890): 50.9 ° C

Production Example 6: Preparation of hexahydrofamesol-1, 2PO-5.0EO

182.4 g of hexahydrofarnesol and 1.7 g of a 44% aqueous KOH solution were placed in a stirred reactor. The mixture dehydrated at 120 ° C and 20mbar for 30 minutes. Subsequently, it was made inert with nitrogen to a pressure of 1.0 bar. At a temperature of 130-140 ° C and a maximum pressure of 2.6 bar 55.8 g of propylene oxide were metered. After a reaction time of 15 minutes at 135 ° C 176.2g of ethylene oxide were metered at a temperature of 163-173 ° C and a maximum pressure of 2.3 bar. After a reaction time of 40 minutes at 165 ° C, the reactor contents cooled to 60 ° C was neutralized by the addition of 0.8 g of acetic acid and the reactor was emptied.

analytics

 OHN = 107.3 mg KOH / g

pH (5% aqueous solution): 6.1

 Cloud point (method E according to DIN EN 1890): 62.0 ° C

Preparation Example 7: Preparation of hexahydrofamesol-4,5PO-2,2EO

159.6 g of hexahydrofarnesol and 2.34 g of a 44% aqueous KOH solution were initially introduced into a stirred reactor. The mixture dehydrated at 120 ° C and 20mbar for 30 minutes. Subsequently, it was made inert with nitrogen to a pressure of 1.0 bar. At a temperature of 125-135 ° C and a maximum pressure of 3.2 bar 184.2 g of propylene oxide were metered. After a post-reaction time of 15 minutes at 130 ° C, 68.8 g of ethylene oxide were metered at a temperature of 145-155 ° C and a maximum pressure of 3.5 bar. After a reaction time of 55 minutes at 150 ° C, the reactor contents cooled to 60 ° C was neutralized by the addition of 1, 1 g of acetic acid and the reactor was emptied.

analytics

 OH = 93.3 mg KOH / g

pH (5% aqueous solution): 7.0

Cloud point (method E according to DIN EN 1890): 41, 8 ° C Production Example 8: Preparation of hexahydrofarnesol-15PO

In a stirred reactor, 91.2 g of hexahydrofarnesol and 0.44 g of a 5% suspension of double metal cyanide catalyst (Zn / cocatalyst were prepared as described in DE 100 08 629 A1 in the comparative example there using Tridekanol N instead of PPG 400 for the suspension) in Tridekanol N submitted. The mixture was dehydrated at 120 ° C and 20mbar for 60 minutes. Subsequently, it was made inert with nitrogen to a pressure of 0.5 bar. At a temperature of 150 ° C and a maximum pressure of 1, 6 bar 348.5 g of propylene oxide were metered. After dosing and an after-reaction time of 30 minutes, the cooled to 80 ° C reactor contents was discharged.

analytics

 OH = 49.6 mg KOH / g

Cloud point (method E according to DIN EN 1890): 8 ° C

C) Application Examples Application Example 1: Shampoo

Shampoo formulation was prepared according to Table 1 below.

Table 1

Application Example 2: Hair Conditioner

A hair conditioner formulation according to Table 2 below was prepared.

Table 2

Composition Quantity [% by weight]

 Cetearyl alcohol 4.00

Glyceryl stearate 0.50 Dicocoylethyl hydroxyethylammonium 0.05 methosulfate

 Propylene glycol 2.50

 Glyceryl oleate 0.70

 Hexahydrofarnesol - 7 EO 0.90

 Water ad 100.0

Application example 3: Liquid detergent

A liquid detergent formulation having a composition according to Table 3 was prepared.

Application Example 4: Washing powder

A detergent formulation having a composition according to Table 4 was prepared.

Table 4

Composition Quantity [% by weight] C 9 -C 13 -alkylbenzenesulfonate 15.50

 Tallow fatty alcohol with an average of 5 EO 0.63

 Sodium perborate monohydrate 20.00

 Ci2-Ci8 sodium grease 0.80

 Polyethylene glycol 4000 5.00

 Sodium carbonate 5.36

 Hexahydrofarnesol - 7EO 6.30

 Copolymer sodium salt of acrylic acid and Ma2,28

 leinsäure

 C 12/18 fatty alkyl sulfate (92% by weight of active substance, 7.26

 3.70% by weight of sodium sulfate, 2.80% by weight of other

 Salts of raw materials and unsulfurised fractions,

 1.50% by weight of water)

 Zeolite A, based on anhydrous active substance 22.52

 Fatty alcohol C 12/14 polyglycoside (78% by weight Ak 5,00

 viv substance, 18% by weight of water glass module 2, 4, 5

 Wt .-% water

 Amorphous sodium silicate 1, 60

 Perfume oil 0.45

 Water 7,30

Application Example 5: Solubilization of a fragrance oil in an aqueous surfactant solution

First, a surfactant solution of the following composition was prepared:

Table 5

30 g of this surfactant solution were initially charged and to this was added an amount of a mixture of 1 part by weight of tea tree oil and 4 parts by weight of hexahydrofarnesol 7EO until clouding of the solubilisate occurred.

Reference is expressly made to the disclosure of the references cited herein.

Claims

 claims

1 . Farnesol alkoxylates of the general formula I R-O - (- A-O-) _x -H (I) in which

 R is an at least partially hydrogenated farnesyl radical,

A is identical or different lower alkylene groups, where the polyoxyalkylene radical (-A-O) _x - may consist of one or more different oxyalkylene blocks, and

 x is an integer value of 1 to 100; and mixtures of such compounds. 2. farnesol alkoxylates according to claim 1, wherein R is a (cis) radical of the formula II

(Met) ₂ C =CH-CH ₂ -CH ₂ -C (Met) = CH-CH 2 -CH 2 -C (Met) = CH-CH 2 - (II)

 3 2 1

 stands in which

 one of the double bonds in positions 1, 2 or 3, or

 two of the double bonds in positions 1, 2 or 3, or

 all three double bonds in positions 1, 2 and 3,

 are hydrogenated; or

 wherein R is a mixture of such partially or fully hydrogenated radicals, optionally additionally containing non-hydrogenated farnesyl radicals.

3. Farnesol alkoxylates according to any one of the preceding claims, wherein

a) the group - (- A-0) _x - represents a polyoxyalkylene radical,

 wherein

 x is a value from 3 to 50; and

 Each A is the same lower alkylene groups;

 or

 A has different meanings and represents at least two different lower alkylene groups, which are randomly distributed over the polyoxyalkylene radical; or

b) the polyoxyalkylene radical - (- A-O) _x - is built up from n oxyalkylene blocks - (- Ai-0) _x i - to - (- A _n - 0) _xn -, where x is equal to the sum x1 + ... + xn and at least two oxyalkylene blocks with respect to the meaning of the alkylene radicals (Ai .... A _n ) and / or with respect to the number of their monomer units (x1 .... xn) differ and where x1 to xn independently of one another integer values of 1 to 50 are. Farnesol alkoxylates according to claim 3, wherein the polyoxyalkylene radical is composed of different oxyalkylene blocks and is selected from the radicals:

- (PO) xi- (EO) x2- (AlkO) x ₃ -H

wherein

 PO is propylene oxide, EO is ethylene oxide and AlkO is C3-Cio-alkylene oxide, x1 is an integer value of 1, 2 or 3;

x2 stands for an integer value of 3 to 50; and

x3 stands for an integer value from 1 to 10.

Farnesol alkoxylates according to claim 4, wherein

x1 is an integer value of 1 or 2;

x2 stands for an integer value of 6 to 9, in particular 7 or 8; and

x3 stands for an integer value from 1 to 5. Process for the preparation of a compound of the general formula I

R-0 - (- A-0-) _x -H (I)

where you are

a) an alcohol of the general formula III

R-OH (III) wherein R has the abovementioned meanings, alkoxylated in the presence of an alkoxylation, in the presence or absence of a solvent and in the presence of at least one Niedrigalkylenoxids or Niedrigalkylenoxid- mixture to obtain a compound of formula I wherein the Group - (- A-O) _x - represents a polyoxyalkylene radical wherein

x stands for a value from 4 to 50 and

Each A is the same lower alkylene groups; or

 A has different meanings and represents at least two different lower alkylene groups, which are randomly distributed over the polyoxyalkylene radical; or b) an alcohol of the general formula III

R-OH (III) wherein R has the meanings given above, alkoxylated in the presence of an alkoxylation catalyst, in the presence or absence of a solvent and in the presence of a first Niedrigalkylenoxids, and the alkoxylation repeated alternation of the lower alkylene oxide (nl), where n is an integer value (such as from 1 to 10),

wherein a compound of formula I is obtained, wherein the polyoxyalkylene radical

- (- AO) x- is constructed of n oxyalkylene blocks - (- Ai-0) _x i - - (- A _n -0) _xn -, where x is equal to the sum x1 + ... + xn and at least two oxyalkylene blocks in terms of meaning of the alkylene radicals (Ai ... A _n ) and / or with respect to the number of their monomer units (x1 xn) and where x1 to xn are independently integer values from 1 to 50.

The method of claim 6 b), wherein

i) the alcohol of the above formula III in the presence of a multimetal cyanide catalyst and in the presence or absence of a solvent and in the presence of propylene oxide to give a propoxylate of the formula IV

R-0- (PO) _x propoxylates, and then ii) the propoxylate so formed with the addition of one of the following blocks further alkoxylated.

The process of claim 7 wherein the multimetal cyanide catalyst is selected from catalysts comprising at least one dimetal cyanide compound of general formula (D) in which

M ^{1 is} a metal ion selected from the group consisting of Zn (II), Fe (II), Co (III), Ni (II), Mn (II), Co (II), Sn (II), Pb (II), Fe (III), Mo (IV), Mo (VI), Al (III), V (IV), V (V), Sr (II), W (IV), W (VI), Cu (II) and Cr (III),

M ^{2 is} a metal ion selected from the group consisting of Sr (I), Mg (II), Zn (II), Fe (II),

Fe (III), Co (III), Cr (III), Mn (II), Mn (III), Ir (III), Rh (III), Ru (II), V (IV), V (V), Co (II), Cr (II), Ti (IV), X is a non-cyanide group which forms a coordinate bond to M ¹ selected from the group consisting of carbonyl, cyanoate, isocyanate, nitrite, thiocyanate and nitrosyl,

 a, b, r, t are integers chosen to satisfy the electroneutrality condition.

The process of claim 8 wherein M ^{1 is} Zn (II) and M ^{2 is selected} from Co (III) and Fe (III). 10. Farnesol alkoxylate-containing reaction product obtainable by a process according to any one of claims 6 to 9.

1 1. Use of at least one compound according to any one of claims 1 to 5 or a reaction product according to claim 10 in washing, rinsing, cleaning or softening compositions; in cosmetic products; in fuels or fuel additive mixtures; in agrochemical compositions; or in papermaking equipment.

12. means selected from detergents, dishwashing detergents, cleaning agents and preservatives; cosmetic means; Preparations for making paper; agrochemical compositions; or fuels or fuel additive mixtures containing at least one compound according to any one of claims 1 to 5 or a reaction product according to claim 10. 13. Processes selected from washing, rinsing, cleaning or softening processes;

 Process for papermaking; or Process for the preparation of agrochemical compositions or fuels or fuel additive mixtures, wherein in this process at least one compound according to one of claims 1 to 5 or a reaction product according to claim 10 is used.

14. Use of a compound according to any one of claims 1 to 5 or one

A reaction product according to claim 10 as a solubilizing agent in aqueous systems / liquids, in particular in the emulsion polymerization.