EP2576498A1

EP2576498A1 - Quaternary dialkanolamine esters

Info

Publication number: EP2576498A1
Application number: EP11718346.7A
Authority: EP
Inventors: Sascha Herrwerth; Burghard Gruening; Hans-Jürgen KÖHLE; Isabella Ulrich-Brehm
Original assignee: Evonik Goldschmidt GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2010-06-02
Filing date: 2011-05-02
Publication date: 2013-04-10
Also published as: DE102010029610B4; US20130071343A1; BR112012030412A2; CN102918022A; DE102010029610A1; CA2801447A1; WO2011151120A1; JP2013530164A

Abstract

The invention relates to novel quaternary ammonium compounds of the esterquat type, to a method for the production thereof, and to the use thereof in formulations.

Description

Quaternary dialkanolamine esters

Field of the invention

The present invention relates to novel quaternary ammonium compounds of the esterquat type, to a process for their preparation, and to the use of these in formulations.

State of the art

In the past, quaternary ammonium compounds ("quats") in the form of mono- and dialkyl quats with one or two long alkyl chains in the molecule have found widespread use in a variety of applications including fabric softeners, antistatic formulations, detergents, skin care products, hair conditioners, and corrosion inhibitors , Ink remover for

Paper and much more.

In the field of hair care products as Monoalkylquats example, the (INCI) Cetrimonium Chloride (eg.

commercially available as VARISOFT ^® 300, Evonik

Goldschmidt GmbH) and (INCI) Behentrimonium Chloride (z. B. commercially available as Varisoft ^® BT 85 Pellets, Evonik Goldschmidt GmbH) and (as dialkyl the (INCI) Dicetyldimonium Chloride z. B. commercially available as Varisoft ^® 432 PPG, Evonik Goldschmidt GmbH) in the

Industry used on a large scale.

In addition to their good properties as conditioners, however, these alkylammonium cations also have some

Disadvantages. These include inadequate biodegradability and unfavorable ecotoxicological

Properties . Especially in the field of skin and hair care products could only conventional quats over the years also establish the so-called esterquats, for example (INCI) Distearoylethyl dimonium chloride, commercially available as Varisoft ^® EQ 65 pellets (Evonik Goldschmidt GmbH) or (INCI) Distearoylethyl

Hydroxyethylmonium Methosulfate, commercially available as Dehyquart F 75 (Cognis).

The generic term esterquat is generally understood to mean di- or trialkanolamines esterified with fatty acids in their salt form.

These quaternized fatty acid alkanolamine ester salts are known substances that can be obtained by relevant methods of preparative organic chemistry. Usually, the production of the esterquats is based on a multi-stage process, in which first by

Reaction of an alkanolamine with carboxylic acids or

corresponding derivatives the esterified tertiary

Alkanolamine is prepared, which is then quaternized with a suitable reagent.

In this connection, reference is made to EP0483195, according to which triethanolamine in the presence of

Partially esterified with fatty acids under hypophosphorous acid, air passes through and then quaternized with dimethyl sulfate or ethylene oxide. The compounds listed there serve as softeners for textiles.

In DE4308794 the production of solid ester quats is described by the quaternization of the

Triethanolaminester in the presence of suitable

Dispersant, preferably fatty alcohols, is performed.

Surveys on this topic can be found, for example, under R. Puchta et al. in tens. Surf. Det., 30, 186 (1993), M. Brock in Tens. Surf. Det., 30, 394 (1993), R. Lagerman et al. in J. Am. Chem. Soc, 71, 97 (1994) or under I. Shapiro in Cosm. Toil., 109, 77 (1994). Esterquats have a more favorable ecotoxicological behavioral profile compared to alkyl quats and also have improved biodegradability than alkyl quats due to the presence of ester linkage.

The environmental compatibility of preparations or their ingredients is becoming increasingly important, on the one hand due to appropriate legal regulations, but above all also due to a changed consumer awareness. Consumers increasingly value products that do not adversely affect the environment. This moves properties such as ecotoxicity or biological

Degradability more and more in the focus of the public. Good biodegradability ensures the

Conversion of substances through biological processes, which usually take place in wastewater treatment. The resulting fragments have an even lower

Risk of environmental damage as the starting materials and are very easy to handle in the conventional methods of treatment of wastewater and solid waste. With insufficient biodegradability, the functionality may become more aquatic over time

Communities are affected.

Many of those currently available on the market

Plasticizers or conditioners whose biodegradability has already been improved, however, fall in effectiveness compared to the

from conventional products.

For example, although the application properties of currently available esterquats are also at a high level Level, however, can not keep up with the application properties of (INCI) Behentrimonium Chloride at longer rinsing times. The desired conditioning

Properties are more rapidly reduced in the ester quats of the prior art by the rinsing process.

Because traditional products require either no effective performance or good environmental performance, there is still a great need for compounds that cover both areas by combining excellent care properties with high environmental performance.

In the field of hair care, the conditioners play an important role. Their job is to protect the hair and repair existing damage.

Many hair damage results from exposing the hair to various environmental stressors on a daily basis, including temperature, humidity, sunlight or air pollution. In addition, chemical hair treatments such as bleaching, dyeing, tinting, smoothing or the use of perm lead to negative

Effects on the hair structure.

For example, in a perm, both the cortex and the cuticle of the hair are attacked. The disulfide bridges of cystine are broken by the reduction step and partially oxidized in the subsequent oxidation step to cysteic acid.

Bleaching not only destroys melanin but also oxidizes about 15-25% of the disulfide bonds of cystine in a mild bleach. In an excessive bleaching, it may even be up to 45% (KF de Polo, A Short Textbook of Cosmetology, 2000, Verlag für chemische Industrie, H. Ziolkowsky GmbH). And even the daily washing, combing and blow-drying of the hair leaves traces. The undesirable consequences are, for example, a rough hair surface, a reduced mechanical stability and an increase in the electrostatic charge. Hair breakage, the formation of "split ends", difficult combing and loss of natural shine are the result.

Conditioners are designed to protect the hair from these negative effects, but should not negatively impact the environment if possible.

For this purpose, the conditioner must be able to raise to the hair. Because of the anionic centers on the hair surface based on protein structures, cationic compounds are a preferred class of conditioning agents because they provide the necessary affinity for the hair. In the case of already existing hair damage, the number of anionic groups is even increased, due to the presence of oxidized protein structures such. As the above cysteic acid. Especially in these damaged areas, cationic conditioning agents can reach their full potential

To be effective. The object of the invention was to remedy or at least reduce at least one disadvantage of the prior art and, in particular, to provide active ingredients which are also effective for long rinsing times on the target surface

remain and continue to be effective. Description of the invention

It has surprisingly been found that the compounds of the general formula (I) described below according to claim 1, a process for their preparation and the described compositions and formulations are able to solve the stated object.

The present invention therefore relates to special quaternary dialkanolamine esters.

Another object of the invention is a process for their preparation and their use in formulations. An advantage of the present invention is that the compounds of the invention already at low

Use quantities to develop a good effect.

Another advantage is that the invention

Compounds are environmentally unimportant. Another advantage is that the inventive

Compounds on keratinic fibers show an improved conditioning effect at longer Abspülzeiten than previously known quaternary ester compounds.

A contribution to the solution of the problem initially posed thus afford quaternary Dialkanolaminester the general formula (I)

(CH ₂ ) _n - (CH;

Y ² formula (I) with Y and Y independently of one another, identically or differently, an alkyl radical having 1 to 6 carbon atoms, a benzyl radical or H,

n = 1 to 4,

A- is an anion, preferably selected from the group

containing, preferably consisting of, chloride, bromide,

Iodide, methylsulfate, tosylate, phosphate, sulfate,

Ethyl sulfate, hydrogen sulfate, lactate, acetate and citrate, preferably chloride and methyl sulfate,

X ¹ and X ^{2 are} independently, identically or differently selected from the groups (a), (b) and (c), these groups consisting of

(a) acyl radicals containing 6 to 14 carbon atoms,

(b) acyl radicals containing from 20 to 24 carbon atoms and (c) acyl radicals containing from 3 to 28 carbon atoms which are not included in the groups (a) or (b), or H, with the provisos that the number average per molecule of the general formula (I)

0.40 to 1.20, preferably 0.60 to 1.10, in particular 0.75 to 1.10 residues of group (a),

0.80 to 1.60, in particular 0.90 to 1.40, in particular 0.90 to 1.25, radicals of group (b) and

0 to 0.20, preferably 0.0010 to 0.10, particularly preferably 0.0050 to 0.02, radicals of the group (c)

are included and

the number average per molecule of the radicals of groups (a), (b) and (c) add up to 2.

It is obvious to the person skilled in the art that the formula (I) is a mixture of various quaternary

Dialkanolaminester is reproduced. The remainder Y and Y is preferably a linear alkyl radical which is preferably unsubstituted

Benzyl radical or H; in particular the radical is selected from the group comprising, preferably consisting of, -CH ₃ , -C ₂ H ₅ , benzyl and H.

n is particularly preferably equal to 2.

The acyl radicals of groups (a) and (b) are preferably saturated.

The acyl radicals of groups (a), (b) and (c) are

especially those of the naturally occurring fatty acids with corresponding chain lengths.

Thus, they preferably contain even numbers of carbon atoms.

Acyl radicals of the group (a) are preferably selected from C ₅ H ₁₁ CO-, C ₇ H ₁₅ CO, C ₉ H ₁₉ CO, C ₁₁ H ₂₃ CO and C ₃ H ₂₇ CO-, preferably from C ₉ H ₁₉ CO and C ₁₁ H ₂₃ CO-, in particular C ₁₁ H ₂₃ CO-.

Since the use of technical lauric acid is particularly preferred, a particularly preferred acyl radical of group (a) is an acyl radical having a chain length of 12

Carbon atoms. In this connection, it is preferred that groups (b) and (c) are assigned correspondingly 0 to 1 wt .-%, preferably 0.02 to 0.50 wt .-% acyl radicals of a fatty acid having a chain length less than 11, preferably of from 6 to 10 carbon atoms and 0 to 1% by weight,

preferably 0.30 to 0.70 wt .-% acyl radicals of a fatty acid having a chain length of greater than 13, preferably 14 to 28 carbon atoms, wherein the wt .-% on the

Total amount of all acyl radicals, which can be derived from the technical lauric acid.

Since the use of technical capric acid is also particularly preferred, a particularly preferred acyl radical is the Group (a) an acyl radical with a chain length of 10

Carbon atoms. In this connection, it is preferred that 0 to 1 wt .-%, preferably 0.02 to 0.50 wt .-% acyl radicals of a fatty acid having a chain length of less than 9, are preferably assigned to the groups (b) and (c) from 6 to 8 carbon atoms and 0 to 1 wt .-%, preferably 0.30 to 0.70 wt .-% of acyl radicals of a fatty acid having a chain length of greater than 11, preferably 12 to 28

Carbon atoms, wherein the wt .-% on the

Total amount of all acyl residues, which can be derived from the technical capric acid.

Acyl radicals of group (b) are preferably selected from

C ₁₉ H ₃₉ CO-, C21H43CO- and C23H47CO-.

Particularly preferred acyl radicals of group (b) form the acyl radicals of a technical behenic acid, with corresponding chain lengths, in particular the radicals C ₁₉ H ₃₉ CO-, C21H43CO-, C23H47CO- in a weight ratio of 4-8 to 85-99 to 0-3. In this context, it is preferred that groups (a) and (c) are respectively assigned 0 to 3% by weight, preferably 0.50 to 1.50% by weight, of acyl radicals of a fatty acid having a chain length of less than 19, preferably 6 to 18, in particular 15 to 18 carbon atoms, 0 to 1 wt .-%, preferably 0.25 to 0.75 wt .-% acyl radicals of a fatty acid having a chain length of 26 carbon atoms, wherein the wt .-% on the Total amount of all acyl radicals, which can be derived from the technical behenic acid.

The acyl radicals of group (c) are preferably determined via carboxylic acids, which are additionally present in technical mixtures of the carboxylic acids which contain the acyl radical of the Determine groups (a) and (b), wherein these technical mixtures were used for the preparation of the esterquats according to the invention. For example, contains technical

Lauric acid (group (a)) still a small proportion

saturated fatty acids with a chain length of more than 15 carbon atoms, whose acyl radicals are then assigned to the groups (b) and (c).

It is inventively preferred that in the

Quaternary dialkanolamine esters of the invention

general formula (I) the molar ratio of the acyl groups of group (a) to acyl groups of group (b) in the number average 1 to 0.6 to 4, in particular 1 to 0.8 to 2.4, especially 1 to 0.8 to 1.7.

Very particular preference is given to esterquats in which the acyl radicals of groups (a) to (c) are determined via the acyl radicals of a mixture consisting of

technical grade lauric acid, in particular EDENOR C1298-100 (Emery Oleochemicals) and

technical behenic acid, in particular EDENOR C2285 (Emery Oleochemicals),

wherein the technical lauric acid can be at least partially replaced by a technical capric acid, in particular EDENOR C1098-100 (Emery Oleochemicals).

Another object of the present invention is a process for the preparation of the inventive quaternary Dialkanolaminester.

The quaternary dialkanolamine esters of the invention are advantageously obtainable by the process described below. The process according to the invention for the preparation of quaternary dialkanolamine esters comprises the process steps

A) reaction, preferably esterification, one

Alkyldialkanolamins in which the two alkanol groups are selected from the group consisting of - CH2OH, - C2H4OH, - C3H6OH and -C4H8OH, in particular - C2H4OH, and the alkyl group is selected from the group consisting of alkyl radicals having 1-6 carbon atoms, in particular linear Alkyl radicals, which are preferably unsubstituted, with a mixture of carboxylic acids consisting of the

Groups,

(d) carboxylic acid containing 6 to 14 carbon atoms,

(e) carboxylic acid containing 20 to 24 carbon atoms and optionally

(f) carboxylic acid containing 3 to 28 carbon atoms which are not contained in the groups (d) and (e),

B) reaction, preferably quaternization, of the product from process step A) with a quaternizing agent selected from the group comprising, preferably consisting of, dialkyl sulfates, alkyl halides and benzyl halides and / or C) neutralization of the reaction mixture with an acid, preferably an organic acid, with the In that, based on all the carboxylic acids of groups (d), (e) and (f), 0 to 10 mol%, preferably 0.5 to 5 mol%, preferably 0.25 to 1.0 mol% carboxylic acids of group (f) be used. Alkyl dialkanolamine used particularly preferably in process step A) is methyldiethanolamine.

The carboxylic acids of group (f) are preferably determined via the carboxylic acids, which are additionally present in technical mixtures of the carboxylic acids of groups (d) and (e), which are used in the process according to the invention. Preferred used in process step B)

Alkyl halides have 1 to 6 carbon atoms, particularly preferred here is methyl chloride; In this context, preferred dialkyl sulfate is dimethyl sulfate. The process steps A) and B) can under the

Expert known and usual process conditions for esterification or quaternization are performed.

In method step A), the preferred method is therefore

Alkyldialkanolamin with a mixture of the claimed fatty acids at 140-200 ° C, optionally with the concomitant use of an esterification catalyst, heated and formed

Distilled water condensation continuously. to

If necessary, the reaction is completed by applying a vacuum and monitoring the progress of the reaction by decreasing the acid number. Detailed instructions on this can be found, inter alia, in DE4111966.

In process step B), the alkyl dialkanolamine ester is preferably reacted, if appropriate in a solvent at 60-120 ° C., with the quaternizing reagent, more preferably with methyl chloride. The

Quaternizing reagent is used in excess in this case, the pressure is regulated between 1-8 bar. After the tertiary amine to the desired Conversion is abreagiert, the excess is on

Quaternizing reagent removed by distillation. A

Detailed instructions on this can be found, inter alia, in EP0643128.

The preferred in the method according to the invention

used carboxylic acids of groups (d), (e) and (f) correspond to the preferred acyl groups of groups (a), (b) and (c) supplying carboxylic acids of the compound of the invention.

Particularly preferred here is the use of a mixture of carboxylic acids consisting of technical lauric acid, in particular EDENOR C1298-100 (Emery Oleochemicals) and technical behenic acid, in particular EDENOR C2285 (Emery Oleochemicals).

Organic acids preferably used in process step C) are selected from the group consisting of

Citric acid, tartaric acid, lactic acid, acetic acid,

Formic acid and glycolic acid.

The pH is preferably adjusted in process step C) to a pH of 3.5 to 5.5, preferably with stirring. This step is preferably done at a

Temperature of in particular 40 - 60 ° C. It is inventively preferred that in the

Process according to the invention per mole of alkyldialkanolamine 0.40 to 1.20 mol, preferably 0.60 to 1.10 mol,

in particular 0.75 to 1.10 mol, carboxylic acid of group (d), 0.80 to 1.60 mol, preferably 0.90 to 1.40 mol,

in particular 0.90 to 1.25 mol, carboxylic acid of group (e) are used. According to the invention, in this connection, it is preferred that the molar ratio of the carboxylic acids used of group (d) to group (e) 1 is from 0.6 to 4,

especially 1 to 0.8 to 2.4, especially 1 to 0.8 to 1.7.

A preferred process according to the invention is characterized in that per mole of alkyldialkanolamine total carboxylic acids of groups (d) and (e) and optionally (f) in an amount of 1.80 to 2.5 mol, particularly preferably 1.85 to 2.2 mol are used.

An inventively preferred method is characterized in that in step B) at least one solvent selected from the group consisting of short-chain alcohols, fatty alcohols, polyols and

Carbonates is used.

Short-chain alcohols in this context are those having a chain length of 2 to 6 carbon atoms, such as, for example, ethanol, butanol, isopropanol, hexanol. A fatty alcohol is used in this context

unbranched or branched monoalcohol with a

Alkyl group of 8 to 30 carbon atoms understood. Preferred fatty alcohols are lauryl alcohol, myristyl alcohol,

Cetyl alcohol, palmoleyl alcohol, stearyl alcohol,

Isostearyl alcohol, oleyl alcohol, elaidyl alcohol,

Petroselinyl Alcohol, Guerbet Alcohol, Arachyl Alcohol,

Gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, preferably technical coconut oil or tallow fatty alcohols having 12 to 18, preferably having 16 to 18 carbon atoms.

Preferred alcohols are short chain,

especially isopropanol.

In process step B) used polyols

especially ethylene glycol, propylene glycol, Dipropylene glycol and butylene glycol, carbonate used is in particular propylene and ethylene carbonate.

It is preferable that the solvent is used in an amount of 0.5 to 50% by weight, preferably 1 to 40% by weight, based on the sum of the amounts by weight of

theoretically expected quaternary ester compound and solvent.

Detailed instructions on this can be found in DE4308794.

Another object of the present invention is a composition containing quaternary invention

Dialkanolamine esters and / or dialkanolamine quaternary esters obtainable by the method described above

process according to the invention, at least one solvent, in particular selected from short-chain alcohols,

Fatty alcohols, polyols and carbonates and optionally at least one carboxylic acid selected from at least one of the groups (d), (e) and (f).

The composition according to the invention preferably consists of the abovementioned components.

Preferably, the solvent constitutes from 0.5 to 50% by weight, preferably from 1 to 40% by weight, based on the total weight of the composition.

The solvents contained in the composition according to the invention are generally derived from the addition of solvent in process step B) of the process according to the invention, so that the preferred solvents mentioned in this context are preferably in the

Contain compositions of the invention. Thus, compositions of the invention contain

preferably fatty alcohols, which are a mixture of different fatty alcohols selected from alcohols with a

Chain length of C12 to C24, more preferably one

Mixture of cetyl (C16) and stearyl alcohol (C18), is.

Particularly preferably contained short-chain alcohol is isopropanol. Preferably contained polyols are in particular ethylene glycol, propylene glycol, dipropylene glycol and

Butylene glycol, preferably contained carbonate

in particular propylene carbonate.

Preferably, the carboxylic acids make up from 0% to 10%

Wt .-%, preferably 0.01 wt .-% - 3 wt .-%, based on the total weight of the composition of.

The carboxylic acids contained in the composition according to the invention are generally derived from the excessively added carboxylic acids in process step A) of the process according to the invention, so that the in this

Context named preferred carboxylic acids are preferably included in the compositions of the invention.

Another object of the present invention is the use of the quaternary invention

Dialkanolamine esters and / or the quaternary

Dialkanolamine esters obtainable by the process according to the invention and / or at least one inventive compound

Composition for the preparation of formulations, in particular of cosmetic or pharmaceutical

Formulations and care and cleaning formulations for use in domestic and industrial environments. In this context, preferred cosmetic or pharmaceutical formulations, in particular skin and

Hair treatment formulations, in particular Hair conditioning formulations. Preferred care and cleaning formulations for use in domestic and industrial environments are in this context

Fabric care agents, such as fabric softener, and hard surface care products, in particular for

Vehicles, watercraft, airplanes, windows and benches, shower enclosures, floors such as carpets, tiles, laminates, parquet, cork floors, marble, stone and

Porcelain stoneware floors, household ceramics such as WCs,

Washbasins, bidets, shower trays, bathtubs, doorknobs,

Fittings, household tools such as washing machines, dryers, dishwashers, sinks made of ceramic or stainless steel, furniture such as tables, chairs, shelves, shelves, windows,

Cookware, dishes and cutlery, tools like

surgical instruments, vacuum cleaners, machines,

Pipelines, tanks and equipment for transport, processing and storage in food processing, such as rinse aids, rinse aid.

Thus, formulations, especially cosmetic or pharmaceutical formulations and care and

Cleaning formulations for use in domestic and industrial environments containing quaternary dialkanolamine esters according to the invention and / or quaternary

Composition, in particular in an amount of 0.1 to 7 wt .-%, preferably 0.5 to 4 wt .-%, particularly preferably 1 to 3 wt .-% based on the total formulation,

in particular aqueous formulations, which preferably have a pH of 3.5 to 5.5, another

Subject of the present invention.

The stated, contained in the formulation 0.1 to 7 wt .-%, preferably 0.5 to 4 wt .-%, particularly preferably 1 up to 3% by weight are added by adding up all actually contained in the formulation according to the invention

Components (inventive quaternary dialkanolamine esters, quaternary dialkanolamine esters obtainable according to the

inventive method and inventive

Composition).

Preferred formulations according to the invention contain no further alkyldialkanolamine esters.

The term "aqueous" in this context means a water content of greater than 50 wt .-%, preferably greater than 75 wt .-%, based on the total formulation.

Preferred formulations according to the invention are cosmetic hair and skin care formulations, in particular

Hair care formulations. Particularly according to the invention

preferred formulations are therefore hair shampoos,

Hair rinses, hair setting, hair dyeing,

Hair care emulsions, hair treatments, aerosol foams,

Hair dyes and hair lotions.

The formulations of the invention may e.g. contain at least one additional component selected from the group of

Emollients,

Co-emulsifiers,

Thickeners / viscosity regulators / stabilizers,

antioxidants

Hydrotropes (or polyols),

Solids and fillers,

Perlglänzadditive,

Deodorant and antiperspirant active ingredients,

insect repellents,

Self, Preservatives,

Conditioning agent,

perfumes,

dyes,

cosmetic agents,

Care additives,

Superfatting agent,

Solvent.

Substances which can be used as exemplary representatives of the individual groups are known to the person skilled in the art and can be used, for example, in the German application DE

102008001788.4 are taken. This patent application is hereby incorporated by reference and thus forms part of the disclosure.

With regard to further optional components and the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. K. Schräder, "Fundamentals and formulas of cosmetics", 2nd edition, pages 329 to 341, Hüthig book publisher

Heidelberg, directed.

The quantities of the respective additives depend on the intended use.

Typical frame formulations for the respective applications are known in the art and are included, for example, in the brochures of the manufacturers of the respective basic substances and active ingredients. These existing formulations can usually be adopted unchanged. in the

If necessary, the desired modifications can be made by simple experiments for adjustment and optimization without complications.

Another object of the present invention is the use of the quaternary Dialkanolaminester and / or the Quaternary dialkanolamine esters obtainable after the

process according to the invention and / or at least one composition according to the invention and / or at least one formulation according to the invention as care product,

in particular as a skin and hair care product, and / or for the conditioning of hair, and / or as a softener.

The term "care product" is understood here to mean a substance which fulfills the purpose of obtaining an object in its original form, the effects of external influences (eg time, light, temperature, pressure, contamination, chemical reaction with others, with the object Aging, fouling, material fatigue, fading, reducing or avoiding or even improving desired positive properties of the article, such as improved hair shine or greater elasticity of the object under consideration the following examples will be the

The present invention is described by way of example, without the invention, the scope of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples.

All concentrations in the application examples are given in percent by weight. For the production of

Formulations were used the usual formulation methods known to those skilled in the art.

The following figures are part of the examples:

FIG. 1: Results of the combing force measurements at 1 min

washout FIG. 2: results of the combing force measurements at 3 min

washout

Examples:

Example 1 Preparation of the Compound 1 452 g (1.33 mol) of technical behenic acid (Edenor C 22 85 GS) are mixed with 265 g (1.33 mol) of lauric acid (Edenor C 12 98-100) and at 80 ° C. melted. 159 g (1.33 mol) of methyldiethanolamine are metered into this mixture and, while stirring, the temperature is slowly increased to 200.degree. Water of reaction is distilled off continuously. After 3 hours, to complete the esterification, a vacuum of about 10 mbar is applied until the acid number (SZ) has fallen to <7 mg KOH / g.

The reaction mixture is cooled to 80 ° C and transferred to a pressure reactor. To 828 g (1.33 mol) of the diester are added 466 g of fatty alcohol C 16-18 (TEGO Alkanol C 16 18) and the mixture is homogenized. Subsequently, 73 g (1.44 mol) MeCl are added so that the reaction temperature is maintained in the range of 80-100 ° C and the pressure max. 5 bar does not exceed. After a reaction time of about 4 hours, the total amine number (GAZ) has dropped to <3 mg KOH / g.

Excess methyl chloride is distilled off in vacuo and bottled the finished product.

Example 2:

524 g (1.54 mol) of technical behenic acid (Edenor C 22 85 GS) are mixed with 265 g (1.54 mol) of capric acid (Edenor C 10 98-100) and melted at 80 ° C. To this

Mixture is metered 184 g (1.54 mol) of methyldiethanolamine and performs the esterification as described above. The SZ of the diester is 5.0 mgKOH / g. 762 g (1.28 mol) of the diester are mixed with 92 g of isopropanol and alkylated in a pressure reactor with 77.5 g (1.54 mol) of methyl chloride. The reaction conditions are used as described above.

After the GAZ has fallen to 1.9 mg KOH / g,

distilled off excess methyl chloride in vacuo and bottled the finished product.

Example 3: Testing of hair treatment compositions using the compounds according to the invention: Example 1 and Example 2.

For the performance assessment, hair tresses were used, which were standardized by a bleaching treatment standardized. For this hairdresser usual products are used. The damage to the hair tresses is described in detail in DE10327871.

For the application assessment, the

Compounds of the invention used in Example 1 and Example 2 in a simple cosmetic formulation.

As reference compounds, the commercially available

Alkylquat (INCI) Behentrimonium Chloride (VARISOFT ^® BT 85

Pellets, Evonik Goldschmidt GmbH) and the commercially available Esterquat (INCI) Distearoylethyl Dimonium

Chlorides (VARISOFT ^® EQ 65 pellets, Evonik Goldschmidt GmbH) used.

The application properties when used in hair rinses were checked in the following formulations (Table 1): Formulation Examples COa la 2a V3a V4a

TEGINACID® C, Evonik

Goldschmidt GmbH 0.5% 0.5% 0.5% 0.5% 0.5% (INCI: Ceteareth-25)

TEGO® Alkanol 16, Evonik

Goldschmidt GmbH 4% 4% 4% 4% 4% (INCI: Cetyl Alcohol))

Example 1 (65% in C 16

- 2.3% - - - fatty alcohol)

Example 2 (90% in 1, 66

- - - - isopropanol)

VARISOFT® EQ 65 pellets, 65% - in C 16 fatty alcohol, Evonik

Goldschmidt GmbH

- - - 2.3% - (INCI: Distearoylethyl

Dimonium chlorides, cetearyl

Alcohol)

VARISOFT® BT 85, 85% in

Isopropanol, Evonik

Goldschmidt GmbH - - - - 1,76% (INCI: Behentrimium

chlorides)

Water, demineralized ad 100,0

Citric acid ad pH 4.0

Tab. 1: Hair conditioner formulations for testing hair conditioning properties. The composition of the test formulations is for

Avoidance of influencing the test results by

(usually available) formulation components deliberately chosen simply. Formulations according to the invention may contain, in addition to the ingredients mentioned and / or instead of the ingredients mentioned, further ingredients. In particular, the combination with others

Ingredients can lead to a synergistic improvement in the described effects. The pretreatment of the hair is done by

Shampoo formulation (Table 2), which contains no

Contains conditioning.

Tab. 2: Shampoo formulation for the pretreatment of

Hairdressing.

Standardized treatment of previously damaged hair strands with conditioning samples:

The hair strands previously damaged as described above are washed with the shampoo formulation from Tab. Here, the hair strands are wetted under running, warm water. The excess water is gently squeezed out by hand, then the shampoo is applied and gently incorporated into the hair for 1 minute (0.5 ml / 2 g

Strand of hair). The hair tress is rinsed for 30 seconds under running warm water. This procedure is repeated a second time, except that final rinsing is for 1 min.

Subsequently, directly after washing the

Hair strands with the hair conditioner formulations from Tab. 1 conditioned.

Here, the rinse is applied and gently incorporated into the hair (0.5 ml / 2 g strand of hair). After a

Dwell time of 1 min, the hair is rinsed for a) 1 min or for b) 3 min. Before the sensory evaluation, the hair is dried in air at 50% humidity and 25 ° C for at least 12 hours. Assessment criteria:

Sensory scores are scored on grades ranging from 1 to 5, with 1 being the worst and 5 the best scoring. The individual test criteria each receive their own rating.

The test criteria are:

Wet combability, wet grip, dry combability,

Dry grip, appearance / shine.

In the following tables, the results of the sensory evaluation of the treatment of the hair strands as described above are a) 1 min rinsing time and b) 3 min rinsing time with the inventive

Formulations la and 2a, the comparative formulations V3a and V4a and the control formulation COa (Control without test substance) compared. a) 1 min rinsing time

Wet combed Wet Dry Moisture handle Combat handle

invention

4.7 4.8 4.6 4.7 Formulation la

invention

4.6 4.8 4.7 4.7 Formulation 2a

Comparative Formulation V3a

4.5 4.5 4.6 4.6 (not according to the invention)

Comparative Formulation V4a

4.6 4.5 4.5 4.5 (not according to the invention)

Control formulation COa

2.0 1.5 2.8 3.3 (placebo) Tab. 3: Results of the conditioning of hair at 1 min rinsing time

b) 3 min rinsing time

Tab. 4: Results of the conditioning of hair at 3 min rinsing time

The results in Table 3 show that the formulations la and 2a according to the invention have very good polymerising properties at 1 min rinsing time, as do the comparative formulations V3a and V4a. The comparative formulations V3a and V4a have expected similar kondi tioning properties at 1 min rinsing time.

The results in Table 4 show that the formulations la and 2a according to the invention have better conditioning properties than the comparison formulation V4a at a rinsing time of 3 min. The

Comparative Formulation V4a comprises, as conditioning compound VARISOFT ^® BT 85 (85% in isopropanol, Evonik Goldschmidt GmbH, INCI: Behentrimonium Chloride), an alkyl quat known for its very good conditioning properties even with long rinsing times. The comparative formulation V3a comprises, as conditioning compound VARISOFT ^® EQ 65 pellets (65% in C 16 fatty alcohol, Evonik Goldschmidt GmbH, INCI: Distearoylethyl Dimonium Chloride, Cetearyl Alcohol), an ester quat, the very good conditioning properties at 1 has min washout (see Tab. 3), but with 3 min rinsing time, a significantly worse conditioning than the inventive esterquats Example 1 and 2 has.

Example 4: Influence of the compounds according to the invention on combing forces of hair

Test conditions:

Measuring device: Diastron MTT 175

Measuring distance: 20 cm

Combing speed: 2000 mm / min

Used strands of hair: length = 23 cm; Width = 1.5 cm;

Weight = 2 g

Measuring conditions: T = 22 ° C. The hair strands are with a residual moisture of 60%, determined by

Weight determination, measured.

The experiments will be European, undamaged,

dark brown hair used. To carry out the

Kämmkraftmessungen this hair in the laboratory

Standard conditions damaged by perm:

1.) 4 g permanent wave solution. / g of hair, 15 min. allow to act, 2 min. rinse under running tap water (T = 35 ° C). (Perming Lsg: Universal Perm, Basler) 2.) 4 g fixer (1 part fixer + 3 parts water) / g hair, 10 min. allow to act, 2 min. Rinse.

(Fixing-Lsg: Foam Fixation Concentrate, Basler) Carrying out the combing force measurement before the treatment with the test formulation:

The previously damaged strands of hair become overnight

air conditioned.

3.) The hair strand is immersed for 1 min in a buffer solution (Na citrate, pH = 6).

4.) The hair strand is combed by hand until no change in Kämmwiderstandes is observed.

5.) The hair strand is attached to the meter and the first Kämmkraftmessung is performed. The measurement is repeated a total of 10 times.

Treatment of the strands:

Per strand of hair will be 0.5 g of each

Test formulation used (2 g hair / 0.5 g solution). The formulation is massaged into the hair for 30 seconds and then for 5 min. left to rest, then 1 min. or 3 min. rinsed under running tap water.

Performing the Kämmkraftmessung after treatment with the test formulation:

Points 3-5 are repeated.

Then the combing work (%) is calculated before and after the treatment with the test formulation. Test formulations used:

The combing forces when used in hair rinses were checked in the following formulations (Table 5):

Tab. 5: Hair conditioner formulations for testing hair conditioning properties.

The following figure shows the results of the

Combining force measurements of the experiments carried out as described above for a) 1 min rinsing time and b) 3 min

Rinsing time with the formulations lb and 2b, the comparative formulations V3b and V4b and the

Control formulation COb (control without test substance) compared. The results in Figure 1 show that the

Formulations lb and 2b according to the invention at 1 min

Rinsing time have a pronounced reduction of the combing forces as the comparative formulations V3b and V4b. The comparative formulations V3b and V4b, as expected, generate a similarly pronounced 1 minute rinsing time

Reduction of combing forces.

The results in Figure 2 show that the

formulations lb and 2b according to the invention at 3 min

Rinsing time to a slightly greater reduction of the combing forces than the comparative formulation V4b have. The comparative formulation containing, as conditioning compound V4b VARISOFT ^® BT 85 (85% in isopropanol, Evonik Goldschmidt GmbH, INCI: Behentrimonium Chloride), a

Alkyl quat, which is known for its strong reduction of combing even at long rinsing times.

The comparative formulation containing, as conditioning compound V3a VARISOFT ^® EQ 65 pellets (65% in C 16

Fatty alcohol, Evonik Goldschmidt GmbH, INCI: Distearoylethyl Dimonium Chloride, Cetearyl Alcohol), an ester quat which has a good reduction of combing forces with 1 min rinsing time (see Fig.2), but with 3 min rinsing time a significantly worse reduction of the combing forces than the Esterquats invention Example 1 and 2 has. Formulation examples:

These formulation examples show that the quaternary compounds according to the invention can be used in a large number of cosmetic formulations.

Formulation Example 1) Pearlized Shampoo

TEXAPON ^® NSO, Cognis, 28% strength (INCI:

Sodium laureth sulfates)

Inventive Example 2 0.25%

Perfume 0.25%

Water 55 ^ 25 "6

TEGO ^® betaine F 50, Evonik Goldschmidt

GmbH, 38% (INCI: Cocamidopropyl 8.00%

Betaine)

TEGO ^® Pearl N 300 Evonik Goldschmidt

GmbH (INCI: Glycol distearate, 2.00%

Laureth-4; Cocamidopropyl betaine)

ANTIL ^® 171 Evonik Goldschmidt GmbH

(INCI: PEG-18 glyceryl 1.50%

Oleate / Cocoate)

NaCl 0.50%

Preservative q. s.

Formulation Example 2) Rinse-off conditioner

Water 92, 0%

TEGINACID® C, Evonik Goldschmidt GmbH

0.5%

(INCI: Ceteareth-25)

Inventive Example 1 2.50%

TEGO ^® Alkanol 1618, Evonik Goldschmidt

5, 00%

GmbH (INCI: Cetearyl Alcohol)

Preservative, perfume q. s. Formulation Example 3) Rinse-off conditioner

Formulation Example 5) Rinse-off conditioner

Formulation Example 7) Rinse-off conditioner

Formulation Example 9) Leave-In Conditioner Spray

Lactic Acid, 80% 0.40%

Water 95, 30%

TEGO ^® Amide S 18, Evonik Goldschmidt

GmbH (INCI: Stearamidopropyl 1,20% Dirnethylamine)

Inventive Example 2 0.30%

TEGIN ^® G 1100 pellets, Evonik

Goldschmidt GmbH (INCI: Glycol 0, 90% Distearate)

TEGO ^® Care PS, Evonik Goldschmidt GmbH

1.60% (INCI: methyl glucose sesquistearate)

TEGOSOFT ^® DEC, Evonik Goldschmidt GmbH

0.30% (INCI: diethylhexyl carbonates)

Preservative, perfume q. s.

Formulation Example 10) Leave-In Conditioner Spray

TAGAT ^® CH-40, Evonik Goldschmidt GmbH

(INCI: PEG-40 Hydrogenated Castor 2.20% Oil)

Ceramide VI, Evonik Goldschmidt GmbH

0.05% (INCI: Ceramide 6 II)

Perfume 0.20%

Water 90, 95%

Inventive Example 2 0.30%

LACTIL ^® Evonik Goldschmidt GmbH (INCI:

Sodium lactate; Sodium PCA; Glycine;

fructose; Urea; Niacinamide; 2.00% inositol; Sodium benzoate; Lactic

Acid)

TEGO ^® betaine F 50 Evonik Goldschmidt

GmbH 38% (INCI: cocamidopropyl 2.30% betaine)

Citric Acid (10% in water) 2.00%

Formulation Example 11) Leave-In Conditioner Foam

Inventive Example 2 0.30%

TAGAT ^® CH-40, Evonik Goldschmidt GmbH

(INCI: PEG-40 Hydrogenated Castor 1.0% Oil)

Perfume 0.30%

TEGO ^® betaine 810, Evonik Goldschmidt

GmbH (INCI: Capryl / Capramidopropyl 2.00% Betaine)

Water 94, 00%

TEGO ^® Cosmo C 100, Evonik Goldschmidt

0.50% GmbH (INCI: Creatine)

TEGOCEL ^® HPM 50, Evonik Goldschmidt

GmbH (INCI: hydroxypropyl 0.30% methylcellulose)

Varisoft ^® 300, Evonik Goldschmidt GmbH

1.0% (INCI: Cetrimonium Chloride)

LACTIL ^® Evonik Goldschmidt GmbH (INCI:

Sodium lactate; Sodium PCA; Glycine;

fructose; Urea; Niacinamide; 0.50% inositol; Sodium benzoate; Lactic

Acid)

Citric Acid, 30% 0.10%

Preservative q. s.

Formulation Example 12) Strong Hold Styling Gel

TEGO Carbomer ^® 141, Evonik Goldschmidt

1.20% GmbH (INCI: Carbomer)

Water 66.70%

NaOH, 25% 2.70%

PVP / VA W-735, ISP (INCI: PVP / VA

16. 00% copolymer

Inventive Example 2 0.30%

Alcohol Denat. 10.50%

TAGAT ^® 0 2 V, Evonik Goldschmidt GmbH

2.00% (INCI: PEG-20 Glyceryl Oleate)

Perfume 0.30%

ABIL ^® B 88183, Evonik Goldschmidt GmbH

0.30% (INCI: PEG / PPG-20/6 Dimethicone)

Preservative q. s.

Formulation Example 13) Personal care product

TEXAPON ^® NSO, Cognis, 28% strength (INCI:

30.00% Sodium Laureth Sulfate)

TEGOSOFT ^® PC 31, Evonik Goldschmidt

0,70% GmbH (INCI: Polyglyceryl-3 Caprate)

Inventive Example 2 0.30%

Perfume 0.30%

Water 53, 90%

TEGOCEL ^® HPM 4000, Evonik Goldschmidt

GmbH (INCI: hydroxypropyl 0.30% methylcellulose)

REWOTERIC ^® AM C, Evonik Goldschmidt

GmbH, 32% (INCI: Sodium 10.00% Cocoamphoacetate)

Citric Acid monohydrate 0.50%

Rewoderm ^® LI S 80, Evonik Goldschmidt

GmbH (INCI: PEG-200 Hydrogenated

2.00% glyceryl palmate; PEG-7 glyceryl

Cocoate)

TEGO ^® Pearl N 300, Evonik Goldschmidt

GmbH (INCI: Glycol Distearate; 2.00% Laureth-4; Cocamidopropyl Betaine)

Formulation Example 14) Mild Foam Bath

Formulation Example 16) Rinse-off conditioner

Water 89.20%

TEGINACID® C, Evonik Goldschmidt GmbH

0.5% (INCI: Ceteareth-25)

VARISOFT ^® EQ 65, Evonik Goldschmidt

GmbH (INCI: Distearyl Dimonium 1.50% Chloride, Cetearyl Alcohol)

Inventive Example 1 2.00%

ABIL ^® Soft AF 100, Evonik Goldschmidt

GmbH (INCI: Methoxy PEG / PPG-7/3 1.00% Aminopropyl Dimethicone)

TEGO ^® Alkanol 1618, Evonik Goldschmidt

5, 80% GmbH (INCI: Cetearyl Alcohol)

Preservative, perfume q. s.

Formulation Example 17) Rinse-off conditioner

Water 91, 50%

TEGINACID® C, Evonik Goldschmidt GmbH

0.5% (INCI: Ceteareth-25)

Inventive Example 2 2.00%

SF 1708, Momentive (INCI:

1.00% amodimethicone)

TEGO ^® Alkanol 1618, Evonik Goldschmidt

5, 00% GmbH (INCI: Cetearyl Alcohol)

Preservative, perfume q. s.

Formulation Example 18) Fabric softener 1

Inventive Example 1 4.00%

Dyestuff, 1% 0.15%

Perfume 0.20%

Water, demin. 94% Formulation Example 19) Fabric softener 2

Inventive Example 2 4.00%

Plantatex HCC 5, 00%

Glycerol (99.5% by weight) 17.00%

Phenonip 0.70%

Water, demin. Ad 100%

Claims

claims

Quaternary dialkanolamine esters of the general formula

(CH ₂ ) _n . (CH;

Y ² formula (I) with

Y ¹ and Y ^{2 are} independent, equal or

different alkyl with 1 to 6

Carbon atoms, a benzyl radical or H,

n = 1 to 4

A- is an anion, preferably selected from the group

containing chloride, bromide, methylsulfate, tosylate, phosphate, sulfate, hydrogen sulfate, lactate, acetate and citrate,

X ¹ and X ^{2 are} independent, equal or

variously selected from groups (a), (b) and (c), these groups consisting of

(a) acyl radicals containing 6 to 14 carbon atoms,

(b) acyl radicals containing 20 to 24 carbon atoms and

(c) acyl radicals containing 3 to 28 carbon atoms, which are not contained in the groups (a) or (b), or H,

with the proviso that the number average per molecule of the general formula (I)

0.40 to 1.20 residues of group (a),

0.60 to 1.60 residues of group (b),

0 to 0.20 residues of the group (c) are included and

2. Quaternary dialkanolamine esters according to claim 1, characterized in that

Acyl radicals of group (a) are selected from C ₅ HnCO-, C ₇ H ₁₅ CO-, C ₉ H ₁₉ CO-, CiiH ₂₃ CO- and Ci ₃ H ₂₇ CO-,

Acyl radicals of group (b) are selected from C ₁₉ H ₃₉ CO-, C ₂ H ₄₃ CO- and C 23 H 47 CO- and

Acyl radicals of the group (c) are selected from acyl radicals of the carboxylic acids which are additionally present in technical mixtures of the carboxylic acids which determine the acyl radical of the groups (a) and (b).

3. Quaternary dialkanolamine esters according to claim 1 or

Claim 2, characterized in that

Acyl radicals of group (a) are selected from C 11 H 23 CO-, acyl radicals of group (b) are selected from C ₁₉ H ₃₉ CO-,

C21H43CO-, C23H47CO- in a weight ratio of

4-8 to 85-99 to 0-3.

4. Quaternary dialkanolamine esters according to at least one of claims 1 to 3, characterized in that

the acyl radicals of group (a) to (c) are determined via the acyl radicals of a mixture consisting of

technical lauric acid and

technical behenic acid.

5. Quaternary dialkanolamine according to any one of claims 1 to 4, characterized in that the molar ratio of the acyl groups of group (a) to Acyl radicals of the group (b) on the average 1 to 0.5 to 4.

6. A process for preparing quaternary dialkanolamine esters comprising the process steps

A) reacting an alkyl dialkanolamine in which the two alkanol groups are selected from the group consisting of, -CH ₂ OH, - C2H4OH, - C3H6OH and - C4H8OH and the alkyl group is selected from the group consisting of alkyl radicals having 1-6 carbon atoms

with a mixture of carboxylic acids consisting of the groups

(d) carboxylic acid containing 6 to 14

Carbon atoms,

(e) carboxylic acid containing 20 to 24

Carbon atoms and optionally

(f) carboxylic acid containing 3 to 28

Carbon atoms not included in the groups (d) and (e)

B) reaction of the product from process step A) with a quaternizing agent selected from the group comprising dialkyl sulfates, alkyl halides and benzyl halides and / or

C) Neutralization of the reaction mixture with a

Acid,

with the proviso that based on all the carboxylic acids of groups (d), (e) and (f) 0 to 10 mol% of carboxylic acids of group (f) are used.

7. The method according to claim 6, characterized in that used in process step A) per mole alkyldialkanolamine

From 0.40 to 1.20 moles of carboxylic acid of group (d) and

0.60 to 1.60 moles of carboxylic acid of group (e)

be used.

8. The method according to claim 6 or 7, characterized

characterized in that per mole of alkyldialkanolamine

Total carboxylic acids of groups (d) and (e) and optionally (f) are used in an amount of 1.80 to 2.5 mol.

9. The method according to any one of claims 6 to 8, characterized in that in process step B) at least one solvent selected from the group consisting of short-chain alcohols, fatty alcohols, polyols and carbonates

is used.

10. Containing composition

Quaternary dialkanolamine esters according to at least one of

Claims 1 to 5 and / or

Quaternary dialkanolamine esters obtainable after one

Method according to at least one of claims 6 to 9,

at least one solvent and optional

at least one carboxylic acid selected from at least one of the groups (d), (e) and (f),

wherein preferably the at least one solvent constitutes from 0.5% to 50% by weight, based on the total weight of the composition.

11. The composition according to claim 10, characterized

characterized in that the solvent is isopropanol or propylene carbonate.

Use of quaternary dialkanolamine esters according to

at least one of claims 1 to 5 and / or

Quaternary dialkanolamine ester obtainable by a process according to any one of claims 6 to 9 and / or at least one composition according to

Claim 10 or 11 for the preparation of formulations, in particular of cosmetic or pharmaceutical formulations and care and cleaning formulations for use in domestic and industrial

Environment..

Formulation, especially cosmetic or

pharmaceutical formulation and care and

Cleaning formulation for use in domestic and industrial environments, containing quaternary

Dialkanolamine esters according to at least one of claims 1 to 5 and / or quaternary dialkanolamine esters

obtainable by a process according to any one of claims 6 to 9 and / or at least one

A composition according to claim 10 or 11, in particular in an amount of 0.1 to 5 wt .-%, preferably 0.5 to 4 wt .-%, particularly preferably 1 to 3 wt .-% based on the total formulation, in particular aqueous

A formulation which preferably has a pH of 3.5 to 5.

Use of quaternary dialkanolamine esters according to

at least one of claims 1 to 5 and / or

Quaternary dialkanolamine ester obtainable after one A method according to any one of claims 6 to 9 and / or at least one composition according to

Claim 10 or 11 and / or at least one

A formulation according to claim 13 as a conditioner, in particular as a skin and hair care product, and / or for the conditioning of hair, and / or as

Fabric softener.