RU2574665C2 - Polyurethane thickener - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of producing polyurethanes having at least two hydrophilic portions S, at least one hydrophilic portion P different from S, at least two terminal hydrophobic portions T and at least two hydrophobic portions D different from T, wherein each portion T is directly bonded to a portion S, each portion S is bonded on at least one side to at least one portion D, each portion P is bonded to at least two portions D, wherein the process is carried out in the presence of at least one alkali or alkali-earth metal salt of a monocarboxylic acid of general formula R-COOH, where R is a hydrocarbon residue with 1-12 carbon atoms. The present invention also relates to polyurethanes obtained using said method, use thereof as a thickener for aqueous compositions, as well as compositions containing such polyurethanes.

EFFECT: obtaining polyurethane thickeners having improved thickening action.

14 cl, 1 dwg, 11 ex, 16 tbl

Description

The present invention relates to a method for producing polyurethanes containing at least three hydrophilic sites, at least four hydrophobic sites, optionally allophanate segments and / or isocyanurate segments, which are obtained in the presence of alkali metal (alkaline earth) carboxylates.

In addition, the present invention relates to polyurethanes thus obtained, their use as a thickener for aqueous formulations, and also to compositions containing such polyurethanes.

Polyurethanes have long been used in numerous fields for various purposes. According to the choice of starting materials and their stoichiometric ratio, polyurethanes with very diverse physicochemical properties are obtained.

Thickeners are used in large volumes to increase the viscosity of aqueous compositions, for example, in the field of cosmetics, human nutrition and animal feeding, pharmaceuticals and for detergents, paints and varnishes. As thickeners, among other things, polyurethanes are also known.

For example, solutions or dispersions of polyurethanes in a water-diluted aqueous or predominantly aqueous phase are called HEUR thickeners (i.e., a hydrophobically modified ethylene oxide urethane copolymer) and have long been used in various fields, for example, to thicken dispersed water-based dyes.

It is assumed that the principle of the thickening action of the HEUR thickener in the above example is that the polyethylene-glycol segments provide compatibility with water, and hydrophobic segments are built in via association with each other and also with dispersed particles of a binder thickened dispersed dye (injected into it a) viscosifying three-dimensional molecular compound.

Thickeners are also used in the field of cosmetic formulations. Thickeners for cosmetic formulations require a sufficient thickening effect even in formulations containing a lot of salts. In addition, such thickeners should form cosmetic formulations with a good texture and an acceptable feel on the skin. They should be given compatibility with numerous other excipients, especially with salts and surfactants, and be developed into the compositions of both the thickener itself and other excipients.

In addition, the thickened compositions should also possess, during prolonged storage under conditions of temperature and pH, essentially rheology and physical and chemical properties. Finally, these thickeners should be obtained economically and without noticeable environmental degradation.

In US patents US 4079028 and US 4155892, among other things, polyurethane thickeners are described. The preparation of the polyurethanes described therein is carried out in the presence of a dibutyltin dilaurate (DBTL) catalyst known in the chemistry of polyurethanes.

In European patents EP 1584331 and EP 1013264, polyurethane thickeners for cosmetic formulations are described. They are obtained in one step by mass interaction of a polyol, polyisocyanate and a fatty alcohol, which, if necessary, can be ethoxylated, and obtained without using a catalyst.

International patent application WO 2006/002813 describes polyurethane thickeners for various uses in aqueous media. These thickeners are prepared from hydrophilic polyols with at least two hydroxyl groups, one or more hydrophobic compounds, for example, long chain alcohols and at least di-functional isocyanates. An excess of NCO groups is used. The catalyst used is 1,8-diazabi-cyclo [5-4-0] undec-7-ene (DABCO).

International patent application WO 02/88212 describes polyurethanes from ethoxylated long chain alcohols and cyclic oligomeric diisocyanates, for example, isocyanurates, as starting materials. The described polyurethanes are prepared without the use of a catalyst.

In European patent EP 725097, a polyurethane thickener is described in which a polyether obtained by alkoxylation of alcohols or alkyl phenols is reacted with polyisocyanates in the presence of DBTL, diazabicyclooctane or tin dioctoate as a catalyst, with the ratio of NCO to OH equivalents ranging from 0, 9: 1 to 1.2: 1. This thickener is proposed to be used in the field of reduced shear, for example, for pouring liquid dispersion paints.

European patents EP 1241198, EP 1241199 and EP 1241200 describe the preparation of polyurethane thickeners in the presence of a DBTL catalyst and using simple polyether polyols or polyether polyols containing urethane groups with functionality> 2 (for example, ethoxylated sugar, glycerol, etc.).

European patents EP 761780 and EP 1111014 describe polyurethane thickeners consisting of polyethylene glycol, diisocyanate and branched, preferably long chain branched alkyl groups as a hydrophobic component. Their preparation is carried out in the melt without the use of a catalyst.

International patent applications WO 2009/135856 and WO 2009/135857 describe water-dispersible polyurethanes with a substantially straight-chain main chain of alternating hydrophilic and hydrophobic regions and their use. The formation of polyurethanes is catalyzed by titanium or zinc compounds.

An object of the present invention is to provide a new thickener for water-containing formulations, especially cosmetic formulations. New thickeners should have the best thickening effect. In addition, the thickening effect of new thickeners, at least, should not be reduced in the presence of salts in aqueous formulations.

Another objective of the invention was to obtain polyurethane thickeners with the described properties, which additionally do not contain tin, as this is desirable for use in cosmetics.

The above problems are solved by the method of producing polyurethanes containing:

I) at least two hydrophilic site S,

II) at least one hydrophilic region P different from S,

III) at least two terminal hydrophobic section T,

Iv) at least two hydrophobic regions D differing from T, wherein

a) each section T is directly connected to section S,

b) at least one section D is attached to each section S at least on one side,

c) at least two sections D are joined to each section P, characterized in that

the preparation of polyurethanes is carried out in the presence of at least one carboxylic acid salt with at least one metal selected from the group consisting of alkali metals, alkaline earth metals and mixtures thereof.

Obtained by the method according to the invention polyurethanes are mixtures containing at least partially described polyurethane structures. The polyurethanes obtained by the process of the invention are preferably water-dispersible. According to the invention, this includes the fact that they can also be emulsified in water or completely or partially soluble in water.

The polyurethanes obtained by the method according to the invention (hereinafter also referred to as the "polyurethanes according to the invention") are preferably at least partially branched. The expression “at least partially branched” means that at least a portion of the polymer molecule is not straight chain, but branching.

Such branches may be present in both hydrophobic and hydrophilic regions.

In one embodiment, at least a portion of the terminal hydrophobic portions T is branched.

In another embodiment, at least a portion of the hydrophobic portions D are branched.

An advantage of the polyurethanes prepared according to the invention is that, through the use of carboxylates of alkaline (alkaline earth) metals, the branching of the polyisocyanates can be carried out in the form of isocyanurate or allophanate structures in situ and, therefore, it is not necessary to use previously prepared isocyanurate and allophanate structures for crosslinking the polyisocyanates. starting compounds. Due to this, firstly, the starting materials are cheaper, and secondly, it is possible to adjust the desired number of such branching points to the necessary extent by the amount of catalyst. In addition, the method according to the invention leads to the formation of crosslinked structures a little faster than the use of pre-prepared isocyanurate or allophanate structures.

The main chain of polyurethanes according to the invention consists of alternating hydrophobic or hydrophilic sites, with hydrophobic and hydrophilic sites alternating, but their size, length and nature may vary. In the polyurethanes of the invention, preferably a hydrophobic site is attached to the hydrophilic site on both sides. These hydrophobic sites can be, regardless of each other, the same or different. Each of the sites may be a short chain or oligomeric or polymer radical. By the expression “attaches to the site” is understood that the attachment is carried out directly, that is, that both of these sites in the polymer molecule are directly adjacent.

Hydrophilic sites

Hydrophilic areas are those that show a pronounced interaction with water. Typically, hydrophilic sites are composed of residues of substances that are themselves hydrophilic.

Typical hydrophilic groups known to the person skilled in the art are, for example, nonionic polyether residues. The polyether residues may be homoalkylene oxide residues or may contain mixtures of various alkylene oxide residues. These various alkylene oxide residues may be randomly distributed or in block form in the polyether residues. Preferred polyether residues are homo ethylene oxide residues. Subsequently, ethylene oxide is also referred to as EO, and propylene oxide is also referred to as PO.

In another embodiment, the polyether residues comprise mixtures of EO and PO residues. They can be in polyester residues distributed statistically or blockwise. In a preferred embodiment, the EO and PO residues are in the form of blocks.

A particularly preferred embodiment includes polyether residues containing at least 50 wt.% Ethylene oxide residues, for example, polyether residues containing more than 50 wt.% Ethylene oxide residues, and propylene oxide residues as other alkylene oxide residues. Most preferably, the polyether residues are composed of ethylene oxide residues.

The hydrophilicity of a substance can be determined, for example, by measuring the turbidity of an aqueous solution.

Hydrophilic sites are preferably water soluble. For the purposes of this invention, a substance is said to be soluble in the liquid phase if, when dissolved in 1 l of the liquid phase, at least 1 g, preferably at least 10 g of the substance at 20 ° C and a pressure of 1 bar, the solution for the human eye is clear, i.e. without visible turbidity. Water-soluble are therefore substances which in an amount of at least 1 g, preferably at least 10 g of the substance at 20 ° C and a pressure of 1 bar when dissolved in 1 liter of water, preferably completely desalted water, the solutions are transparent to the human eye, that is, without apparent turbidity.

Hydrophobic sites

By the method of the invention, polyurethane molecules are obtained which contain at least two terminal hydrophobic regions T and at least two hydrophobic regions D.

However, depending on how the reaction is carried out, polyurethane molecules are also obtained containing two hydrophobic region T and only one hydrophobic region D.

Typically, hydrophobic sites consist of residues of substances that are not miscible or poorly miscible with water and are preferably simultaneously lipophilic, i.e. readily soluble in non-polar solvents, such as, for example, fats and oils.

Typical hydrophobic T sites are, for example, hydrocarbon residues, especially long chain hydrocarbon residues.

In one embodiment, hydrocarbon residues are unbranched.

In another embodiment, the hydrocarbon residues are branched.

In yet another embodiment, the polyurethanes of the invention contain both branched and unbranched hydrocarbon residues.

Long chain aliphatic alcohols, aromatic alcohols, as well as aliphatic diisocyanates are examples of hydrophobic substances, the remains of which may be contained in the hydrophobic regions of the polyurethanes of the invention.

Obtained by the method according to the invention, the polyurethanes contain at least two end hydrophobic sections (T), which, regardless of each other, can be the same or different.

In a preferred embodiment, at least a portion of the polyurethanes of the invention comprise more than two terminal hydrophobic sites (T).

The terminal hydrophobic portions of T may be branched or unbranched. Preferably, at least one of the two terminal hydrophobic portions T is branched.

The terminal hydrophobic portions T preferably contain at least one alkyl residue. This alkyl residue preferably contains from 4 to 30 carbon atoms, especially from 8 to 30 carbon atoms, and most preferably from 12 to 30 carbon atoms.

The main chain length of the alkyl residues contained in the T sites is preferably in the range of 4 to 30 carbon atoms. These are, for example, alkyl residues of straight or branched alkanes, such as, for example, butane, isobutane, pentane, isopentane, neopentane, hexane, heptane, octane, 2-ethylhexane, nonane, decane, undecane, dodecane, tridecane, isotridecan, tetrade , pentadecane, hexadecane, heptadecane, octadecane, nonadecane, ikozan, genicosan, docosan, tricosan, isotricosan, tetracosan, pentacosan, hexacosan, heptacosan, octacododecodode 2-decodecodode 2-decodecodode 2 .

The hydrophobic sites T may also contain residues of cycloalkanes and cycloalkenes, such as are described, for example, in European patent EP 761780 A2, page 4, lines 56-58; alkene residues, for example, as described in European patent EP 761780 A2, page 4, lines 51-52 or alkylaryl residues, such as described, for example, in European patent EP 761780 A2, page 4, lines 53-55.

Plots T, particularly preferably contain the previously described alkyl residues with 8-30 carbon atoms, most preferably from 12 to 30 carbon atoms.

Plots T consist (or contain) preferably of the previously described aliphatic residues, however, they may also contain or consist of the previously described aromatic residues.

Preferably, at least one portion of T is a branched alkyl residue.

In a preferred embodiment, the side chains of branched alkyl radicals have a chain length of at most 6, preferably at most 4 carbon atoms.

In one embodiment, the branches are clearly shorter than the main chain. In yet another embodiment, each branch of region T of the polyurethanes of the invention has a chain length corresponding to a maximum of half the main chain length of this region T. In a preferred embodiment, the branched alkyl radicals are iso- and / or neoalkyl radicals. In one preferred embodiment, isoalkanes are used as branched alkyl residues. Particularly preferred is an alkyl residue with 13 carbon atoms, especially an isoalkyl residue with 13 carbon atoms.

In another embodiment, the T sites contain branched alkyl residues whose side chains have at least 4 carbon atoms, preferably at least 6 carbon atoms.

The introduction of sections of T in the polyurethane according to the invention can be carried out in various ways.

In a preferred embodiment, sites T are introduced into polyurethanes simultaneously and together with hydrophilic sites S through the use of alkoxylated alcohols.

Suitable alcohols are, for example, alkoxylated:

- straight chain alcohols from natural sources or obtained by the Ziegler reaction of ethylene in the presence of aluminum alkyl catalysts. Examples of suitable alcohols are alcohols with 6-30 carbon atoms, especially alcohols with 12-30 carbon atoms. Particularly preferred alcohols include n-dodecanol, n-teradecanol, n-hexadecanol, n-octadecanol, n-eicosanol, n-docosanol, n-tetracosanol, n-hexacosanol, n-octacosanol and / or n-three -actanol, as well as mixtures of the above alcohols, for example, NAFOL® types, such as NAFOL® 22+ (Sasol);

- oxoalcohols, such as, for example, isoheptanol, isooctanol, isononanol, isodecanol, isoundecanol, isotridecanol (for example, Exxal® - types 7, 8, 9, 10, 11, 13);

- alcohols branched in position-2; this refers to the Guerbet alcohols known to the specialist, which are obtained by dimerizing primary alcohols by the so-called Guerbet reaction. Particularly preferred alcohols include lsofol®12 (Sasol), Rilanit® G16 (Cognis);

- alcohols obtained by Fidel-Kraft alkylation with oligomerized olefins and containing, in addition to a saturated hydrocarbon residue, an aromatic ring. Particularly preferred alcohols include i-octylphenol and i-nonylphenol;

- alcohols of the general formula (4) according to European patent EP 761780 A2, page 4:

or alcohols of the general formula (5) according to European patent EP 761780 A2, page 4:

moreover

- R ⁴ , R ⁵ , R ⁷ and R ^8, independently of one another, have the meanings indicated in European patent EP 761780 A2, page 4, lines 45-58; R ⁴ , R ⁵ , R ⁷ and R ^8, independently of one another, are preferably alkyl residues with at least 4 carbon atoms, and the total number of carbon atoms in the alcohol is a maximum of 30;

- R ⁶ is an alkylene radical, such as, for example, —CH ₂ -, —CH ₂ —CH ₂ -, —CH ₂ —CH (CH ₃ ) -;

As an example of the corresponding alcohol, 2-decyl-1-tetradecanol can be mentioned.

In one embodiment, mixtures of ethoxylated fatty alcohols with 16-18 carbon atoms are used to introduce T sites into polyurethanes.

In another embodiment, ethoxylated 13-carbon alcohols or mixtures thereof are used to introduce T sites into polyurethanes.

In yet another embodiment, mixtures containing ethoxylated fatty alcohols with 16-18 carbon atoms and ethoxylated isoxoalcohols with 13 carbon atoms are used to introduce T sites into polyurethanes.

In a further embodiment, the alcohols of the general formula (4) and (5) described above according to European Patent EP 761780 A2, page 4 in their ethoxylated form are used to introduce T sites into polyurethanes.

Of course, that additional can also be introduced into polyurethanes and other sections T.

Naturally, hydrophobic T sites can also be incorporated into polyurethanes by any mixtures of the ethoxylated alcohols described above.

Of course, as in the polymerization reaction mixtures of different polymers are usually obtained, so in the method according to the invention mixtures of different polyurethanes are also obtained. As used herein, the term “polyurethane” can mean either each individual polyurethane molecule or a combination of polyurethane molecules produced by the method of the invention.

Obtained by the method according to the invention, the polyurethanes are preferably mixtures containing the described polyurethane structures.

In accordance with this invention also relates to the production of mixtures of polyurethanes whose terminal hydrophobic sites T are branched and / or unbranched alkyl radicals. The invention also relates to the production of mixtures containing polyurethanes having both branched and unbranched, end hydrophobic portions T.

Preferably, at least a portion of the polyurethane molecules produced by the method of the invention comprises allophanate segments. The invention also relates to a method for producing polyurethanes according to the invention, wherein at least a part of the obtained polyurethanes contains polyurethane allophanate structures.

Preferably, at least a portion of the polyurethane molecules produced by the method of the invention comprises isocyanurate segments.

A subject of the invention is also the method of the invention, wherein at least a portion of the polyurethane contains isocyanurate segments.

Hydrophilic S

In the polyurethanes obtained by the method according to the invention, hydrophilic sites S are attached to the terminal hydrophobic portions T. S portions in the polyurethanes, independently of each other, can be the same or different, straight-chain or branched.

In one embodiment, the hydrophilic sites S have different lengths and are straight chain.

Sites contain preferably alkylene oxide residues. Preferably, the number of alkylene oxide residues is in the range of 2 to 150, particularly preferably it is 5 to 100 alkylene oxide residues, and most preferably in the range of 10 to 100 alkylene oxide residues.

The hydrophilic sites S preferably contain ethylene oxide residues or consist of ethylene oxide residues. In a preferred embodiment, the hydrophilic sites S contain ethylene oxide residues (EO units), the number of which is in the range of 2 to 150 EO units, particularly preferably in the range of 5 to 100 EO units, and most preferably in the range of 10 to 100 EO units.

In a preferred embodiment, sections S are composed of 5-30, preferably 10-25 EO units.

In another preferred embodiment, S sections are comprised of 30-100, preferably 40-100 EO units.

The number of EO units in the molecule of ethoxylated alcohol is called the degree of ethoxylation.

Preferably, the ethoxylated alcohols used in the process of the invention have an ethoxylation degree in the range of 2 to 150 ethylene oxide residues, preferably in the range of 5 to 100 ethylene oxide residues, and even more preferably in the range of 10 to 100 ethylene oxide residues.

In a particularly preferred embodiment, the ethoxylated alcohols used have a degree of ethoxylation ranging from 10 to 25 ethylene oxide residues.

In one embodiment, a branched non-ionic compound of the structural formula RO (CH ₂ CH ₂ O) _x H is used as at least one alcohol, wherein R is an alkyl radical with 13 carbon atoms, preferably an isoalkyl radical with 13 carbon atoms and x = 3, 5, 6, 6, 5, 7, 8, 10, 12, 15, or 20, preferably x = 10. One of these ethoxylated alkyl branched alcohols is, for example, the commercial product Lutensol® TO10.

In one embodiment, the alcohol of general formula (4) according to European patent EP 761780 A2, page 4 is used as at least one alcohol:

or an alcohol of the general formula (5) according to European patent EP 761780 A2, page 4:

moreover

- R ⁴ , R ⁵ , R ⁷ and R ^8, independently of one another, have the meanings indicated in European patent EP 761780 A2, page 4, lines 45 to 58; preferably, R ⁴ , R ⁵ , R ⁷ and R ⁸ are independently from each other alkyl residues with at least 4 carbon atoms, and the total number of carbon atoms in the alcohol is a maximum of 30;

- R ⁶ is an alkylene radical, such as, for example, —CH ₂ -, —CH ₂ —CH ₂ -, —CH ₂ —CH (CH ₃ ) -.

As an example of the corresponding alcohol, 2-decyl-1-tetradecanol can be mentioned.

In one embodiment of the invention, mixtures of ethoxylated straight chain and ethoxylated branched long chain alcohols are used, especially mixtures of the above types of alcohols.

In one embodiment, the hydrophilic sites S comprise EO and PO units.

S sites may also contain long chain alkylene oxide radicals, provided that S sites must be hydrophilic in the aggregate. Hydrophilicity can be controlled, for example, by the number of EO units in section S.

Hydrophobic Sites D

At least one hydrophobic region D is attached to each hydrophilic region S. Moreover, region S may also be contained within the polyurethane molecule of the invention. In this case, this region S is connected not as an extreme region S to region D and region T, but at least on two sides is connected to regions D. Preferably, region S in the molecule is connected to each region D on both sides.

For all sections S located at the edge, the rule applies that they are directly connected to the terminal section T. If section S is to be slightly branched, then it can be directly connected in two or more places to hydrophobic sections D. Preferably, if to each hydrophilic section S. At least one side joins the hydrophobic section D.

In a particularly preferred embodiment, all sections S are unbranched and extreme and are connected on the one hand with section T, and on the other hand with section D.

By the method of the invention, polyurethane molecules containing at least two hydrophobic regions D are obtained. Depending on how the method of the invention is carried out, polyurethane molecules containing only one hydrophobic region D are also obtained.

In polyurethane molecules with at least two hydrophobic regions D, these regions may be the same or different independently of each other.

Plots D may be branched with short chain hydrophobic branches or unbranched. Preferably, at least a portion of portions D is branched. Sites D preferably contain at least one hydrophobic chain of carbon atoms, the length of which is in the range from 2 to 20 carbon atoms, preferably from 3 to 16 carbon atoms and, in particular, in the range from 4 to 12 carbon atoms.

Plots D preferably contain diisocyanate residues. Particularly preferably, sections D contain residues of aliphatic diisocyanates. Thus, for example, a hydrophobic region D may consist of one or more aliphatic diisocyanate residues. Section D preferably consists of one to ten aliphatic diisocyanate residues, particularly preferably one to five aliphatic diisocyanate residues, most preferably it contains one, two or three aliphatic diisocyanate residues.

Hydrophobic residues D may contain aliphatic diisocyanate residues with long, medium length, or short aliphatic units.

In one preferred embodiment, sections D of the polyurethanes prepared by the process of the invention are cycloaliphatic or aliphatic diisocyanate residues.

Particularly preferred sites D are aliphatic diisocyanate residues. As aliphatic diisocyanates, for example, 1,4-butylenediisocyanate, 1,12-dodecamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 2,4,4- or 2,2, 4-trimethylhexamethylene diisocyanate and especially hexamethylene diisocyanate (HDI).

As cycloaliphatic diisocyanates, for example, isophorondiisocyanate (IPDI), 2-isocyanatopropylcyclohexyl isocyanate, 4-methyl-cyclohexane-1,3-diisocyanate (H-TDI) and 1,3-bis (isocyanatomethyl) -cyclohexane can be mentioned.

As residues, so-called H ₁₂ -MDI or, in the English version, called “saturated MDI” diisocyanates, for example, such as 4,4′-methylene bis (cyclohexyl isocyanate) (alternatively called also dicyclohexylmethane-4,4′-diisocyanate) or 2,4′-methylenebis (cyclohexyl) diisocyanate.

Of course, to obtain mixtures of various polyurethanes in the method according to the invention can be used mixtures of the above and the above diisocyanates.

In a preferred embodiment, a portion of the polyurethanes prepared by the process of the invention comprises hydrophobic regions D with allophanate structures. Allophanate structures are formed by attaching an isocyanate group to the urethane unit.

In one preferred embodiment, a portion of the polyurethanes prepared by the process of the invention comprises hydrophobic regions D with isocyanurate structures. Isocyanurate structures are formed by the addition of three isocyanate groups (trimerization).

In another preferred embodiment, a portion of the polyurethanes prepared by the method of the invention comprises both hydrophobic regions D with allophanate structures and hydrophobic regions D with isocyanurate structures.

In another preferred embodiment, a portion of the polyurethanes prepared by the method of the invention comprises hydrophobic regions D with biuret structures. Biuret structures are formed by attaching an isocyanate group to the urea unit. Urea units are again formed by the addition of primary amines to isocyanate groups.

Hydrophilic P

By the method of the invention, polyurethane molecules are obtained containing at least one hydrophilic region P different from the hydrophilic regions S. The rule is that at least two hydrophobic regions D are joined to the region P. The regions P of the polyurethanes according to the invention can be independently from each other the same or different.

Depending on how the method of the invention is carried out, additional polyurethane molecules are obtained that do not contain hydrophilic sites P.

If the polyurethane according to the invention does not contain more than one region P, then between the hydrophilic regions P, in each case, there is at least one hydrophobic region D. If, however, the polyurethane according to the invention contains more than one region P, then they can be the same or different .

The polyurethanes according to the invention can contain, in one embodiment, between two hydrophilic regions P, a sequence of regions from the sequence of a hydrophobic region D, then a hydrophilic region S, then again a hydrophobic region D. If more than one region P is contained in the polyurethane according to the invention, then the regions inside the molecule have the following alternation of sites: PDP or PDSDP. If more than two P sites are to be contained, then both sequences are possible in one molecule.

Preferably, the molecule of the polyurethane obtained according to the invention contains only one or two sites P.

The hydrophilic sites P are introduced into polyurethanes, preferably through the use of hydrophilic polyols. They contain in the molecule at least two hydroxyl groups OH and at least two functional groups selected from the functional groups —O— (ether groups) and —COO— (ester groups), the molecular weight of these hydrophilic compounds being at least at least 300 and preferably at least 1200.

One embodiment of the invention is a method according to the invention, characterized in that at least one hydrophilic region P has a number average molecular weight of from 1,500 to 20,000 g / mol, preferably from 4,000 to 12,000 g / mol.

Suitable hydrophilic polyols are, for example, ethylene oxide polymerization products, their mixed polymerization products or their grafted polymerization products, as well as the polyether obtained by condensation of polyhydric alcohols or mixtures thereof and by ethoxylation of polyhydric alcohols, amides, polyamides and amino piers. Examples thereof are, for example, polyethylene glycols, products of the addition of ethylene oxide to trimethylolpropane, block copolymers of ethylene oxide (EO) and propylene oxide (PO), a hydroxyl-terminated polyester, such as, for example, polyester such as polyfunctional polycaprolactones.

Preferred hydrophilic polyols are polyether polyols. They are such hydrophilic polyols which contain at least two hydroxyl groups and at least two functional groups —O— (ether groups) in the molecule. These simple polyether polyols, in any case, are so hydrophilic that they are water soluble at room temperature (20 ° C).

For the preparation of polyurethanes by the method according to the invention, those polyether polyols are preferably suitable which contain mainly polyethylene glycol. It is especially preferred if these polyethylene glycols contain in the molecule an average amount of ethylene oxide units (EO) in the range of 30 to 450.

Preferred are the polyols of the general formula HO- (CH ₂ —CH ₂ —O) _n —H, and n can range from 30 to 450. Polyethylene glycols, which are condensation products of ethylene oxide with ethylene glycol or water, are meant. The molecular weight of these polyethylene glycols is preferably in the range of from 1500 to 20,000 g / mol.

However, ethylene oxide (EO) and propylene oxide (PO) block copolymers can also be used to introduce P sites into the polyurethanes prepared according to the invention. For example, block copolymers of the general formula HO- (EO) _m - (PO) _n - (EO) _o -H are used, with m and o being independent of each other, are integers ranging from 10 to 100, preferably from 20 to 80, n means an integer ranging from 5 to 50, preferably from 20 to 40, with m, n and o being selected so that the HO- (EO) _m - (PO) _n - (EO) block copolymer _o -H was water soluble.

The substantially straight chain polyester moieties according to the invention preferably have a number average molecular weight M _n of at least 1,500 g / mol and a maximum of 20,000 g / mol.

In a preferred embodiment, the substantially straight chain polyester moieties have a number average molecular weight in the range of 1500 g / mol to 150,000 g / mol.

In another preferred embodiment, the substantially straight chain polyester moieties have a number average molecular weight in the range of 4000 g / mol to 12000 g / mol.

In a particularly preferred embodiment, the substantially straight chain polyester moieties have a number average molecular weight in the range of 6000 g / mol to 10000 g / mol.

In yet another particularly preferred embodiment, the straight chain polyester moieties have a number average molecular weight M _{n of} about 10,000 g / mol.

In another particularly preferred embodiment, the straight chain polyester moieties have a number average molecular weight M _{n of} about 6000 g / mol.

All hydrophilic regions of the polyurethanes prepared by the process of the invention, i.e., regions S and P, can be polyether residues.

In a preferred embodiment, the hydrophilic sites of the polyurethanes according to the invention consist of:

- polyalkylene oxide units (sections P) and

- polyethylene oxide units (sections S).

In a particularly preferred embodiment, in the polyurethanes prepared by the process of the invention, all of the P and S sections are composed of ethylene oxide EO units.

By the method of the invention, polyurethane molecules are obtained containing at least three hydrophilic sites. In one embodiment, they are two S sites and at least one P.

Depending on how the reaction is carried out, however, additionally polyurethane molecules are also obtained with only two hydrophilic sites S which do not contain hydrophobic sites P.

Preferably according to the invention, the method according to the invention also obtain polyurethanes:

I) containing at least two hydrophilic site S,

II) not containing hydrophilic sites P,

III) containing at least two terminal hydrophobic section T,

Iv) comprising at least one hydrophobic portion D different from section T,

moreover

a) to each section T joins section S,

b) to each section S joins section D.

Obtained by the method according to the invention polyurethanes, additionally containing allophanate structures, preferably have at least three sections S and at least one section P.

However, depending on the reaction, polyurethanes containing allophanate structures and at least three S sites but not containing P sites are also additionally prepared.

Obtained by the method according to the invention, polyurethanes, additionally containing isocyanurate structures, have at least three sites S and at least one site P.

However, depending on how the reaction is carried out, polyurethanes containing isocyanurate structures and at least three S sites, but not containing P sites, are also further prepared.

At least a portion of the polyurethanes prepared by the process of the invention are straight chain and have the following sequence of sections: T-S-D-P-D-S-T and T-S-D-P-D-P-D-S-T. Depending on how the reaction is carried out, polyurethanes having a sequence of T-S-D-S-T sections are also further prepared.

In a preferred embodiment of the invention, at least a portion of the polyurethanes prepared by the method of the invention contains allophanate and / or isocyanurate structures and has the following sequence of sites:

Obtained by the method according to the invention, polyurethanes, additionally containing allophanate structures, can have, for example, the following structure:

Obtained by the method according to the invention, polyurethanes containing additionally isocyanurate structures can have, for example, the following structure:

For each P site, it matters that its molecular weight exceeds the molecular weight of each S site contained in the same molecule.

The ratio of the number average molecular weight M _{n of} each of the hydrophilic sites S of the polyurethanes of the invention to the molecular weight of each of the hydrophilic sites P is in the range from 1: 1.4 to 1: 140, preferably in the range from 1: 1.7 to 1: 120.

In a preferred embodiment, this ratio is 1: x, wherein x is equal to or greater than 2, preferably equal to or greater than 2.3, and particularly preferably equal to or greater than 2.8. Most preferably, this ratio is in the range of 1: 2.8 to 1: 115, especially in the range of 1: 3 to 1:95, and most preferably in the range of 1: 3.4 to 1:80.

Typically, mixtures of various polyurethanes are prepared by the process of the invention. Such mixtures may, for example, contain polyurethanes, which although they have the same sequence of sections T, S, D and / or P, but in at least one of the sections they are structurally different from each other. As an example of this, various site structures or various site chain lengths can be mentioned. Thus, in the mixture obtained by the method according to the invention of polyurethanes, the T portions can vary. For example, mixtures of the polyurethanes of the invention may contain polyurethanes in which all sections of T are branched, and / or may contain such polyurethanes in which all sections of T are straight chain, and / or may contain such polyurethanes that contain at least one straight chain section T, and at least one branched section T.

In one embodiment, the sum of the molecular weights of all T sites with the molecular weights of D sites remains less than or equal to the molecular weights of all P sites.

Catalyst

To obtain polyurethanes by the method according to the invention, salts of carboxylic acids and alkali metals, salts of carboxylic acids and alkaline earth metals, or mixtures thereof are used as a catalyst.

Carboxylic acids whose alkali or alkaline earth metal salts are used in the process of the invention are preferably monocarboxylic acids of the general formula RCOOH, in which R may be any organic residue, for example an aliphatic, aromatic or heterocyclic residue.

Preferably, R is an aliphatic residue, for example, an alkyl, alkenyl or alkynyl residue. R may also contain heteroatoms, for example, carboxylic acids may also be hydroxy carboxylic acids.

In a preferred embodiment of the invention, R is a hydrocarbon residue with 1-20 carbon atoms, preferably with 1-12 carbon atoms. R may be a straight chain or branched, saturated or unsaturated residue.

In one embodiment of the invention, the carboxylic acid is acetic acid.

In another embodiment of the invention, the carboxylic acid is octanoic acid.

In a further embodiment of the invention, the carboxylic acid is 2-ethylhexanoic acid.

In yet another embodiment of the invention, the carboxylic acid is neodecanoic acid.

In another embodiment, the carboxylic acid is n-decanoic acid.

In one embodiment of the invention, the carboxylic acid is stearic acid.

In yet another embodiment, the carboxylic acid is ricinoleic acid ((9Z, 12K) -12-hydroxy-9-octanoic acid).

In a further embodiment of the invention, the carboxylic acid is hydroxycarboxylic acid, such as, for example, citric or lactic acid, especially lactic acid.

If at least one alkali metal salt with a carboxylic acid is selected as a catalyst, the alkali metal is preferably selected from sodium and potassium, particularly preferably potassium.

If at least one alkaline earth metal salt with a carboxylic acid is selected as a catalyst, the alkaline earth metal is preferably selected from calcium or magnesium, particularly preferably calcium.

In a preferred embodiment of the invention, potassium acetate is used as a catalyst for producing polyurethanes by the method of the invention.

In another preferred embodiment of the invention, potassium lactate is used as a catalyst for producing polyurethanes by the method of the invention.

Of course, for the preparation of the polyurethanes (PU) of the invention, mixtures of two or more salts of alkali and alkaline earth metals with carboxylic acids can also be used as a catalyst.

In a preferred embodiment, a single catalyst is used.

In addition to these catalysts, other catalysts known to those skilled in the art of polyurethane production may be used.

The catalysts commonly used in polyurethane chemistry are organic amines, especially tertiary aliphatic, cycloaliphatic or aromatic amines and Lewis acids - organic metal compounds.

As Lewis acids, organic metal compounds, metal complexes, for example, acetylacetonates of iron, titanium, zinc, aluminum, cobalt, manganese, nickel and zirconium, such as zirconium-2,2,6,6-tetramethyl- are used, for example. 3,5-heptanedione. Other metal compounds are described by Blank et al. In Progress in Organic Coating, 1999, 35, 19 ff.

Bismuth, cobalt or zinc catalysts as well as cesium or titanium salts can also be used as catalysts.

In one embodiment of the invention, the amount of such other catalysts that are not alkali or alkaline earth metal salts with carboxylic acids and their salts is a maximum of 10 wt.%, Preferably a maximum of 5 wt.%, Most preferably a maximum of 1 wt.% And, especially a maximum of 0, 1 wt.% Of the total amount of catalyst.

In one embodiment of the invention, the method of the invention is characterized in that the preparation of the polyurethane is carried out in the presence of at least 10 ppm. tin.

In another embodiment, the method of the invention is characterized in that the preparation of the polyurethane is carried out in the presence of at least 10 ppm. zinc.

In another embodiment of the invention, in addition to at least one carboxylic acid salt with at least one metal selected from alkali metals, alkaline earth metals or mixtures thereof, no other catalysts are used to produce polyurethanes.

The catalyst or mixture of catalysts is preferably used in an amount ranging from 50 ppm. up to 5000 ppm calculated on the total weight of all reagents. Preferably, the catalyst is used in an amount ranging from 50 ppm. up to 2,500 ppm, particularly preferably in an amount ranging from 100 ppm up to 1000 ppm calculated on the total weight of all reagents.

Depending on the properties of the catalyst, it is added to the reaction mixture in solid or liquid form. A suitable solvent is a non-aqueous solvent, such as, for example, aromatic or aliphatic hydrocarbons, inter alia, toluene, xylene, ethyl acetate, hexane and cyclohexane, as well as a carboxylic acid ester such as ethyl acetate. Further suitable solvents are acetone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethyl acetate (DMC) and N-methylpyrrolidone and N-ethylpyrrolidone.

The catalyst / mixture of catalysts is preferably used in soluble form, particularly preferably dissolved in polyether polyols, by means of which hydrophilic sites of P. are introduced into the polyurethanes.

The catalyst may already be contained at least partially in the polyether polyols used for the method according to the invention, since alkali or alkaline earth metal salts of carboxylic acids have been used or have been formed.

In one embodiment, the polyetherdiols used in the process of the invention also contain, if necessary, at least a portion of the required total amount of catalysts.

In one embodiment of the invention, the polyetherdiols used in the method of the invention already contain at least a portion of the required catalyst before starting the process, and the remainder is added to carry out the process.

In the method for producing polyurethanes according to the invention, preferably the following starting products are used:

A) compounds incorporating hydrophilic sites of P into polyurethanes: preferably polyols of the general formula HO- (CH ₂ —CH ₂ —O) _n —H, wherein n preferably has a value of from 30 to 450; this refers to polyethylene glycols, which are the condensation products of ethylene oxide with ethylene glycol or water. Polyethylene glycols preferably have a number average molecular weight of from 6,000 to 12,000 g / mol, particularly preferably a number average molecular weight of from 6,000 to 10,000 g / mol;

B) compounds introducing terminal hydrophobic portions T into polyurethanes and adjacent hydrophilic portions S respectively to sites T: preferably ethoxylated C ₁₆ -C ₁₈ fatty alcohols, ethoxylated iso-C ₁₃ -oxy alcohols, ethoxylated branched alcohols according to Production Examples 1 to 24 European patent EP 761780 A2 and mixtures thereof;

C) compounds incorporating hydrophobic sites D into polyurethanes: aliphatic diisocyanates, in particular hexamethylene diisocyanate (HDI).

In one embodiment, the method of producing polyurethanes according to the invention comprises the following steps:

I) obtaining a mixture containing:

a. at least one simple polyetherdiol with a molecular weight in the range from 6000 to 12000 g / mol;

b. at least one alkyl branched C ₈ -C ₃₀ -, preferably C ₁₂ -C ₃₀ alkanol, ethoxylated by 10 to 100 mol, preferably 10 to 40 mol, even more preferably 10 to 25 mol of ethylene oxide per mole of alkanol ;

c. at least one carboxylic acid salt with at least one alkali or alkaline earth metal, preferably potassium carboxylate.

II) if necessary, heating the mixture from stage I) to a temperature of from 60 to 120 ° C, preferably to a temperature of from 80 to 100 ° C;

III) if necessary, reducing the water content in the mixture to a water content of a maximum of 1000 ppm, preferably a maximum of 300 ppm, in each case, based on the total weight of the mixture;

IV) adding to the mixture at least one diisocyanate, preferably hexamethylene diisocyanate;

V) carrying out the reaction of the resulting reaction mixture to an isocyanate content of a maximum of 0.1 wt.% Based on the total weight of the reaction mixture.

By a reaction mixture is meant a combination of all substances that are in the reaction space after a point in time to which the entire amount of catalysts, isocyanates, a reaction incapable of isocyanates of substances, and all other substances, such as, for example, solvents, have been fully introduced.

Solvents mean liquid phases at a temperature of 20 ° C and a pressure of 1 bar, in which one or more of the starting products for producing polyurethanes are soluble at 20 ° C and a pressure of 1 bar, as well as substances introducing hydrophilic and / or hydrophobic sites into polyurethanes or acting as a catalyst.

In one embodiment of the invention, the amount of solvents different from substances incorporating hydrophilic and hydrophobic sites into polyurethanes or acting as a catalyst is in the range from 0 to 10 wt.%, More preferably from 0 to 5 wt.% And in particular from 0 up to 1 wt.% in each case, based on the weight of the reaction mixture.

In yet another embodiment of the invention, the method according to the invention is carried out mainly in the absence of solvents other than substances introducing hydrophilic and / or hydrophobic sites into the polyurethane, or acting as a catalyst,

In a further embodiment of the invention, the amount of such substances which, after complete addition of all substances during the reaction, are present in the reaction space and are neither catalysts nor substances that are introduced into the resulting polyurethanes and thereby form hydrophilic and hydrophobic sites in them and which are not reaction products, is a maximum of 10 wt.%, preferably a maximum of 5 wt.%, more preferably a maximum of 1 wt.% and, most preferably a maximum of 0.1 wt.% of the total all substances present during the reaction in the reaction space.

Simply put, the reaction mixture in the preferred embodiment does not contain any other substances, except substances that introduce hydrophilic or hydrophobic sites into the polyurethanes, reaction products, if necessary, a small amount of water and catalysts.

The preferred method, in which in addition to the starting products for the formation of polyurethanes do not use another solvent, leads to a faster reaction and it is not necessary to separate the solvent.

Another advantage of avoiding the use of solvents, especially organic solvents, which differ from substances introducing hydrophilic or hydrophobic sites into polyurethanes or acting as a catalyst, is the better acceptability of the obtained polyurethanes for use as components of cosmetic formulations.

Since the method according to the invention still uses solvents that are different from substances introducing hydrophilic or hydrophobic sites into polyurethanes or acting as a catalyst, they are completely removed, if possible, after the reaction. "After the reaction" means the point in time at which the content of isocyanate groups is still a maximum of 0.1 wt.% Of the total mass of the reaction mixture.

One-step method

In a preferred embodiment, the method is carried out in one step.

“One-step” in this case means that substances with groups reactive with isocyanate groups are mainly brought into contact with substances containing isocyanate groups simultaneously and simultaneously.

In a preferred embodiment of the invention, therefore, the mixture of substances with reactive groups is brought into contact with substances containing isocyanate groups.

Moreover, by the beginning of the reaction in the reaction space, the total amount of all substances with groups reactive with isocyanate groups is brought into contact with substances containing isocyanate groups. Such a process is described, for example, in example 10 of European patent EP 761780 A2 on page 4, lines 29-47 and in subsequent examples 11-24.

The difference of the one-stage method is that all types of substances with groups reactive with isocyanate groups are at any time near each other. However, it is not necessary that the quantitative ratio of various substances in the mixture be constant.

In contrast to the two-step reaction, in the one-step reaction, the polyol is not first reacted with an excess of polyisocyanate, resulting in the formation of prepolymers with the structure -DPD- and -DPDPD with isocyanate end chains, which in the second stage interact with ethoxylated alcohol, resulting in the formation of structures -TSDPDST and -TSDPDPDST.

In a preferred one-step reaction, first, in addition to the structures -T-S-D-P-D-S-T and -T-S-D-P-D-P-D-S-T, the structures -T-S-D-S-T are also formed.

However, for the one-step process, it is not necessary that by the beginning of the reaction the entire amount of all substances with groups reactive with isocyanate groups is already in the reaction space. It is also possible that at the beginning of the reaction only part of each of the substances with groups reactive with isocyanate groups were present in the reaction space, and each residue of the substances was added during the reaction.

In a two-stage process in the first stage, the predominant amount of substances with several groups reactive with isocyanate groups is brought into contact with substances containing isocyanate groups, and substances with only one group reactive with isocyanate groups react in the second stage with remaining isocyanate groups and form the end chains of polyurethanes.

In the one-stage method, the number of polymers with the -T-S-D-S-T structure exceeds their amount in the two-stage method, while in the two-stage method, the number of polymers with the -T-S-D-P-D-S-T structure is higher.

In a preferred embodiment, the polyurethanes obtained by the method of the invention are transferred to the aqueous phase, if necessary, after separation of the solvent.

It is useful if, after transferring the reaction product to water, the resulting mixture is stabilized.

Suitable radical scavengers are, for example, hydroxy-TEMPO, 2,6-di (tert-butyl) -p-cresol (Kerobit® TBK), hydroquinone monomethyl ether, tocopherol and mixtures of these compounds. These stabilizers are used in amounts ranging from 5 to 500 ppm. based on the weight of the aqueous mixture.

It is also useful to use preservatives. Suitable preservatives are, for example, phenoxyethanol, methylisothiazolinone, ethylhexylglycerol, 3-acetyl-6-methyl-2H-pyran-2,4 (3H) -dione, benzoic acid, parabens and mixtures of these substances. Preservatives are used in amounts ranging from 0.1 to 1 wt.% Based on the aqueous mixture.

Preferably, the method of the invention uses substances with groups reactive with isocyanate groups that are substantially water free to inhibit the competing reaction of the isocyanate groups with water. Removing the water of these substances in the method according to the invention can be carried out by azeotropic distillation, drying under vacuum or other methods known to the specialist. Water is removed, for example, to a water content of substances of a maximum of 500 ppm, preferably a maximum of 300 ppm.

Preparation for the actual reaction can be carried out in such a way that substances with groups reactive with isocyanate groups are kept under reduced pressure, preferably under vacuum, and thus water is substantially removed.

Water-containing substances can also be mixed with a solvent, such as xylene, toluene or acetone, and water can be removed along with the added solvent by azeotropic distillation.

In the method of the invention, the molar ratio of the polyetherdiols used to the diisocyanates used is in the range of 1: 1.1 to 1: 2. Preferably, this ratio is in the range of 1: 1.1 to 1: 1.9. Particularly preferably, this ratio ranges from 1: 1.1 to 1: 1.8. Most preferably, this ratio ranges from 1: 1.2 to 1: 1.75. Of course, this ratio can also be 1: x, where x is greater than or equal to 1.3, preferably x is greater than or equal to 1.5.

In one embodiment, it turns out that the molecule obtained according to the invention polyurethanes preferably contains only one or two sites P.

In another embodiment of the method according to the invention, in addition to the said limits, the ratio of polyetherdiols to diisocyanates, the ratio of polyetherdiols to ethoxylated alcohols, is chosen so that the molar ratio of the used polyetherdiols to the used ethoxylated alcohols is in the range from 5: 1 to 1: 2. Preferably, this ratio is in the range of 2: 1 to 1: 2, particularly preferably in the range of 1.5: 1 to 1: 2, and most preferably about 1: 1.

For a particularly preferred method according to the invention, it is important that the molar proportion of polyetherdiols, diisocyanates and ethoxylated alcohols is in the range of 1: 1.2-1.75: 1-2 and especially 1: 1.5: 1.

The invention also relates to a process according to the invention, characterized in that at least one ethoxylated alcohol with 4-30 carbon atoms, one polyether diol and one diisocyanate are used in the production of polyurethanes.

Preferred is a method characterized in that at least one alcohol with 4-30 carbon atoms is a branched alcohol with 12-30 carbon atoms, at least one polyether diol has an average molecular weight M _{n of} from 4000 to 12000 g / mol, and at least one diisocyanate is an aliphatic diisocyanate.

The invention also relates to the use of the polyurethanes of the invention for the preparation of aqueous formulations. Preferred are compositions containing at least 5 wt.% Water, especially at least 20 wt.% Water, more preferably at least 30 wt.% Water and most preferably at least 70 wt.% Water

Preferred are compositions containing a maximum of 95 wt.% Water, particularly preferably a maximum of 90 wt.% Water and in particular a maximum of 85 wt.% Water.

Water-containing formulations may be, for example, solutions, emulsions, suspensions or dispersions.

In addition to the polyurethanes obtained by the method according to the invention, other substances can be used to obtain the compositions, such as, for example, conventional excipients (e.g. dispersant and / or stabilizers), surfactants, preservatives, antifoams, fragrances, wetting agents, UV filters, pigments, emollients, biologically active substances, other thickeners, dyes, plasticizers, water retention agents and / or other polymers.

Obtained by the method according to the invention, polyurethanes and mixtures thereof are preferably used for effective and stable thickening of compositions with a salt and pigment content of more than 1 wt.% Based on the composition. In this case, the term “stable” means maintaining a higher viscosity compared to an ungelled state over a period of several weeks and / or maintaining the viscosity of the composition with increasing temperature, for example, to 50 ° C.

Obtained by the method according to the invention, the polyurethanes exhibit their thickening effect even at elevated temperatures up to about 50 ° C.

In addition, the polyurethanes obtained by the method according to the invention exhibit a thickening effect in a wide range of pH values from 2 to 13.

The polyurethanes obtained by the method according to the invention, in addition, affect the structure of the compositions in which they increase the dispersion of the particles dispersed in them, that is, reduce the size of their particles.

The polyurethanes obtained by the method according to the invention, in addition, affect the structure of the compositions in which they increase the dispersion of the particles dispersed in them, that is, reduce the size of their particles.

Obtained by the method according to the invention, polyurethanes and mixtures thereof can also be used in order to obtain water-containing compositions comprising at least one salt and at least one surfactant or mixtures thereof. Surfactants in connection with the present invention also mean emulsifiers, as well as mixtures of surfactants and emulsifiers. Salts in connection with the present invention are understood to mean salts and salt-like structures even with low pKs and mixtures thereof.

Particularly preferably, the polyurethanes prepared by the process of the invention are used to prepare formulations containing at least 0.05 wt.% Salt and / or at least 0.5 wt.% Surfactants, most preferably at least 0.1% ( w / w) salts and / or at least 1 wt.% surfactants.

In one embodiment, the polyurethanes prepared by the process of the invention are used to formulate compositions containing at least 5 wt.% Salt, preferably at least 10 wt.% Salt.

In another embodiment, the polyurethanes prepared by the process of the invention are used to formulate compositions containing up to 25 wt.% Surfactants, preferably up to 20 wt.% Surfactants, and particularly preferably up to 15 wt.% Or less surfactants.

In yet another embodiment, the polyurethanes prepared by the process of the invention are used to prepare formulations containing at least 1 wt.% Salt and up to 20 wt.% Surfactants, preferably up to 15 wt.% Surfactants.

Particularly preferably, the polyurethanes prepared by the process of the invention are used to formulate oil-in-water emulsions.

Typically, oil-in-water emulsions contain oil in the range of more than 0 to 40% by weight. Preferably, the oil-in-water emulsions according to the invention are obtained with an oil content in the range of 5 to 40% by weight, especially in the range of 10 to 35% by weight and in particular 15 to 30% by weight.

Most preferably, the polyurethanes prepared by the process of the invention are used to formulate oil-in-water emulsions and, in addition, contain at least one salt.

The compositions of the invention containing the polyurethanes prepared by the method of the invention can be, for example, solutions, emulsions, suspensions or dispersions.

In one embodiment, the composition of the invention is a dispersion, preferably an aqueous dispersion, of the polyurethanes prepared by the method of the invention, such as can be obtained after the manufacturing process by treatment from reaction products. For this, for example, water is added to the reaction mixture after the reaction and a dispersion is obtained. If necessary, preservatives and / or suspensions may also be added.

In one embodiment, the dispersion according to the invention contains up to 50 wt.% Obtained according to the invention polyurethanes.

In another embodiment, the dispersion according to the invention contains up to 25 wt.% Solid.

Most preferably, the aqueous dispersions contain up to 25% by weight of the polyurethanes prepared according to the invention, at least one of the previously described cosmetic preservatives and, optionally, at least one of the cosmetic stabilizers described above.

In another embodiment, the polyurethane obtained according to the invention is in powder form. Such a powder can be obtained by spray drying or freeze drying.

To obtain the compositions of the invention, which can be, for example, solutions, emulsions, suspensions or dispersions, the polyurethanes of the invention are preferably used in the form of aqueous dispersions or in the form of a powder, such as can be obtained, for example, by appropriate treatment of the polyurethanes after the process for their preparation.

Other ingredients may be contained in the compositions of the invention, depending on the intended use.

Compositions containing the polyurethanes of the invention may contain other thickeners. These other thickeners are known to those skilled in the art. Suitable thickeners are described, for example, in Kosmetik und Hygiene von Kopf bis Fuβ, Hrsg. W. Umbach, 3. Auflage, Wiley-VCH, 2004, S. 235-236. Other suitable thickeners for the compositions of the invention are also described from page 37, line 12 to page 38, line 8 of international patent application WO 2006/106140. The contents of these text are hereby referenced in full.

In one embodiment of this invention, no thickeners other than the polyurethanes of the invention are used to prepare the compositions of the invention.

Preferred are the polyurethanes of the invention, a 10 wt.% Aqueous dispersion of which at a shear rate of 100 s ⁻¹ has a dynamic viscosity (as measured above) of at least 100 mPa · s, particularly preferably at least 200 mPa · s and most preferably at least 300 MPa · s.

Aqueous dispersions of the polyurethanes prepared by the method of the invention can exhibit either Newtonian or structural viscosity properties. The structural viscosity of 10 wt.% Aqueous dispersions containing the polyurethanes obtained by the process of the invention has a shear rate of 100 s ⁻¹ , a dynamic viscosity of at least 1000 mPa · s, particularly preferably at least 3000 mPa · s.

Specialists know that in water-containing formulations, many thickeners lose their effectiveness, that is, the viscosity of the composition decreases if the compositions contain salts or surfactants. In contrast, the polyurethanes of the invention provide stable viscosity to aqueous formulations even when salts and / or surfactants are added.

Particularly preferred are the polyurethanes of the invention, which, at a salt concentration of at least 0.5% by weight, after their addition, stabilize the dynamic viscosity (measured as described below) of the aqueous compositions containing them.

Particularly preferred are those polyurethanes that provide stable dynamic viscosity even when at least 0.5 wt.% Salt is added and at least 1 wt.% Surfactants are added.

In another embodiment, the presence of the polyurethanes of the invention in salt-containing aqueous formulations leads to an increase in viscosity compared to compositions containing only the salt or only polyurethanes of the invention.

Moreover, the sequence in which polyurethane and salt are added does not matter.

Particularly preferred are the polyurethanes of the invention, leading to an increase in the dynamic viscosity of aqueous, salt and / or surfactant-containing formulations.

Particularly preferred are the polyurethanes of the invention, which lead to an increase in the dynamic viscosity of the aqueous composition at a salt concentration of greater than or equal to 0.5% by weight.

Preferred are the polyurethanes of the invention, leading to an increase in dynamic viscosity at a salt concentration in the aqueous composition of at least 0.05 wt.%. Particularly preferred are the polyurethanes of the invention, leading to an increase in dynamic viscosity compared with compositions containing less than 0.05 wt.%, Preferably less than or equal to 0.01 wt.% Salt, or containing less than 0.5 wt.%, Preferably less or equal to 0.1 wt.% surfactant.

Another advantage of the polyurethanes obtained by the process of the invention is micelle formation in water. The critical concentration of a substance for micelle formation, also called the critical concentration of micelle formation (in English, "Critical Micelle Concentration", CMC), is the concentration of a substance, mainly a substance having hydrophobic and hydrophilic sites, at which spontaneous micelles with an average particle size of less than or equal to 200 nm, especially less than or equal to 100 nm (when determined by dynamic light scattering (as described below), the critical micellization concentration (CMC) of the polyurethane s according to the invention in water (when determined as described below), is preferably less than or exactly 1 g / l, particularly preferably less than or exactly 0.5 g / l, even more preferably less or exactly 0.25 g / l and, most preferably less than or exactly 0.1 g / l.

Another advantage of the method according to the invention of the obtained polyurethanes and compositions according to the invention is the use of alkaline or alkaline earth carboxylates as catalysts in the preparation of polyurethanes and, consequently, the simultaneous rejection of the use of catalysts that are doubtfully suitable cosmetically.

In the field of cosmetic formulations, a known method using tin is no longer desirable since tin may be contained in the products and compositions prepared from them.

The use of alkaline or alkaline-earth carboxylates as catalysts for the method according to the invention provides the in situ formation of allophanate and isocyanurate structures and, as a result, the economically favorable formation of branched hydrophobic sections D of polyurethanes. Due to the branched sections D can be obtained polyurethane thickeners with increased efficiency.

The polyurethanes according to the invention, due to their tolerance to a high salt content and at the same time high surfactant content, as well as to extreme pH values, can also be advantageously used as a thickener in household compositions, such as, for example, liquid detergents.

The polyurethanes of the invention are also particularly suitable as a rheological modifier for formulations containing hydrogen peroxide.

Cosmetic Compounds

The compositions obtained according to the invention are preferably used in cosmetic compositions. The invention also relates to cosmetic compositions containing the polyurethanes obtained according to the invention.

One embodiment of the invention are water-containing cosmetic formulations comprising the polyurethanes prepared according to the invention.

The compositions of the invention can be in the form of aqueous or aqueous-alcoholic solutions, in the form of emulsions, preferably oil-in-water emulsions (O / W), as well as water-in-oil emulsions (W / O) , hydrodispersion formulations, stabilized solids formulations, cosmetic pencil formulations, PIT formulations, in the form of cream, foams, sprays (pump sprays or aerosols), gels, gel sprays, lotions, oils, oil gels or mousses and, accordingly, may be formulated using other conventional excipients.

Preferably, the compositions of the invention are in the form of a gel, foam, mousse, spray, ointment, cream, suspension emulsion, lotion, milk or paste.

The invention preferably relates to cosmetic compositions selected from gels, gel creams, milk, hydraulic formulations, compositions for cosmetic pencils, cosmetic oils and oil gels, masks, tanning products, face care products, body care products, preparations after sun exposure exposure. By the term “cosmetic formulations” is also meant oral care formulations.

Other cosmetic compositions according to the invention are cosmetic compositions for the skin, in particular compositions for skin care. They can be, for example, in the form of water-in-oil skin creams (W / O) or, preferably, oil-in-water type creams (O / W), day and night creams, eye creams, face creams, anti-wrinkle creams, facial creams, moisture retention creams, bleaching creams, vitamin creams, skin lotions, skin care lotions and moisture-holding lotions.

Other preferred formulations according to the invention are face masks, cosmetic lotions and formulations for use in decorative cosmetics, for example, for concealers, theater paints, masks and eyeshadows, lipsticks, eye liners, eyeliner, makeup, primers, blush, powder, eyebrow pencils.

Other formulations of the invention are acne and acne remedies, repellents, shaving products, hair removal products, intimate care products, foot care products, and baby care products.

Further preferred formulations of the invention are detergents, shower and bath preparations. The washing, showering and bathing preparations of the present invention are liquid and gel soaps, clear soaps, luxury soaps, creams, soaps for babies, soaps for skin protection, abrasive soaps and synthetic detergents, paste soaps, soaps - Ointments and washing pastes, liquid detergents, preparations for shower and bath, such as washing lotions, products and shower gels, bath shampoos, preparations for oil baths and scrubs, shaving foams, lotions and shaving creams.

Cosmetic formulations containing special polyurethanes are described, for example, in international patent application WO 2009/135857. The polyurethanes prepared according to the present invention are suitable mainly for use in the compositions described in international patent application WO 2009/135857. Reference is made to the publication of the international patent application WO 2009/135857.

In the framework of the present invention, the polyurethanes used in the compositions of the international patent application WO 2009/135857 are replaced by the polyurethanes of the present invention. The polyurethanes of the invention are preferably also used in the compositions of international patent application WO 2009/135857 instead of the polyurethanes used therein.

Suitable ingredients for the compositions of the invention are described in international patent application WO 2009/135857, pages 24-35, which is hereby incorporated by reference in its entirety.

According to the invention, a cosmetic UV light stabilizer, for example, contains the polyurethanes obtained according to the invention. By cosmetic light stabilizer is meant according to this invention cosmetic compositions containing at least one UV filter, preferably several UV filters.

UV light stabilizers corresponding to the UV light barrier composition of the invention are described in international patent application WO 2009/135857 pages 35-42, to which reference is made in full.

The invention also relates to cosmetic compositions, preferably in liquid or paste form, for use on the skin, mucous membranes and especially on keratin-containing substrates, such as hair, eyelashes and eyebrows, especially for shaping, decorating, coloring, giving a beautiful look, as well as for the care of skin and areas adjacent to the skin. The compositions according to the invention can be used mainly with appropriate adjustment and coloring, also as makeup, camouflage, camouflage, eyeshadow, for eyeliner, lip, blush, lipstick, lip gloss, sunscreen, sun blocker, for temporary tattoos, for spectacular colored sunscreen for surfers and the like.

A preferred embodiment of the present invention are also cosmetic compositions for decorative cosmetics.

Compositions corresponding to the compositions of the invention for decorative cosmetics are described in international patent application WO 2009/135857, pages 43-46, to which reference is hereby made in full.

The object of the present invention are aqueous compositions containing, in addition to the polyurethanes obtained according to the invention, at least one salt and / or surfactant.

Another embodiment of the invention are shampoos and cosmetic cleansers containing the polyurethanes prepared according to the invention.

Compositions corresponding to shampoos and cosmetic cleansers according to the invention are similar to those described in international patent application WO 2009/135857, pages 46-55, to which reference is made in full.

Another embodiment of the invention are deodorants or antiperspirants containing the polyurethanes prepared according to the invention, especially deodorant lotions and deodorant and antiperspirant pencils, dispersions or emulsions of the oil-in-water (O / W) type for applying biologically active substances, especially biologically water-soluble, to the skin active substances.

The compositions corresponding to the deodorants and antiperspirants according to the invention are similar to those described in international patent application WO 2009/135857, pages 55-59, to which reference is made in full.

Another embodiment of the invention is a hair dye containing the polyurethanes obtained according to the invention.

Suitable compositions for dyeing hair compositions containing the polyurethanes obtained according to the invention are similar to those described in international patent application WO 2009/135857, pages 59-65, to which reference is made in full.

Another embodiment of the invention is hair care products, especially hair conditioners containing the polyurethanes prepared according to the invention.

Hair care products containing the polyurethanes prepared according to the invention are similar to those described in international patent application WO 2009/135857, pages 59-67, to which reference is made in full.

Another embodiment of the invention are acidic formulations containing the polyurethanes prepared according to the invention.

Numerous cosmetic formulations contain biologically active substances, the desired effect of which develops at an acidic pH value. These include, for example, formulations containing alpha-hydroxycarboxylic acids (AHA) and beta-hydroxycarboxylic acids (BHA), since in the neutral state they are ineffective or ineffective. Acid formulations corresponding to acid formulations containing the polyurethanes prepared according to the invention are similar to those described in international patent application WO 2009/135857, pages 67-69, to which reference is made in full.

Another embodiment of the invention are products for tanning, containing obtained according to the invention polyurethanes.

Commercial tanning products are typically oil-in-water (O / W) emulsions. The aqueous phase in them is stabilized by means of emulsifiers used in cosmetics.

Thanks to the use of the products according to the invention for tanning the skin, it is possible not only to achieve uniform coloring of the skin, but at the same time it is also possible to uniformly color the areas of the skin that differ in color or due to a painful measurement.

As tanning agents according to the invention, glycerol aldehyde, hydroxymethyl-glyoxal, γ-dialdehyde, 5-hydroxy-1,4-naphthoquinone (yuglon), and also 2-hydroxy-1 obtained from henna leaves are preferably used 4-naphthoquinone. Most preferred is 1,3-dihydroxyacetone (DHA), a triatomic sugar formed in the human body. 6-Aldo-D-fructose and ninhydrin may also be used as a tanning agent according to the invention. By means of a tanning agent according to the invention, skin coloring other than a brown tone is also meant.

In a preferred embodiment of the invention, such compositions contain self-tanning agents in a concentration of from 0.1 to 10 wt.% And particularly preferably from 0.5 to 6 wt.%, In each case, based on the total weight of the composition.

Preferably, these compositions contain 1,3-dihydroxyacetone as an auto-tanning agent. These compositions also contain, preferably organic and / or inorganic light filters. The compositions may also contain inorganic and / or organic and / or modified inorganic pigments.

Other ingredients which are preferably contained in the compositions of the invention are named, for example, in German patent DE 10321147 in sections [0024] to [0132], which is hereby incorporated by reference in its entirety.

The invention also relates to the use of such compositions for staining the skin of multicellular organisms, especially human and animal skin, in particular also for leveling the color of variously pigmented skin areas.

Another embodiment of the invention are compositions for the care of the oral cavity and teeth and their cleaning, containing obtained according to the invention polyurethanes.

Compositions containing the polyurethanes obtained according to the invention for the care of the oral cavity and teeth and their cleaning are similar to those described in the international patent application WO 2009/135857, pages 69-70, to which reference is made in full.

Another embodiment of the invention are hair removal formulations containing the inventive polyurethanes.

Compositions containing the polyurethanes obtained according to the invention for hair removal are similar to those described in international patent application WO 2009/135857, pages 70-71, to which reference is made in full.

The next embodiment of the invention are compositions containing polyurethanes prepared according to the invention for permanent shaping of hair.

Permanent hair formulations containing the polyurethanes obtained according to the invention are similar to those described in international patent application WO 2009/135857, pages 71-73, to which reference is made in full.

Examples

The invention is explained in more detail by the following non-limiting examples.

Unless otherwise indicated, percent data is mass percent data.

Dynamic viscosity determination

The dynamic viscosity of the polyurethanes according to the invention, in each case, was determined in a 10% by weight aqueous solution at 23 ° C. For this, in the examples below, dynamic viscosity was always measured at a shear rate of 100 s ^-1 to 350 s ^-1 . These two indicators make it possible to judge whether the polyurethanes of the invention exhibit a structural-viscosity and Newtonian thickening effect in an aqueous dispersion.

To determine the dynamic viscosity according to DIN 53019 used:

- Rotational viscometer Physica Rheolab MCI Portable (firm Anton Paar);

- cylindrical measuring system, Z4 DIN Zylinder (diameter 14 mm);

Subsequently named polyols, ethoxylated alcohols and isocyanates were used essentially in an alkali-free form (potassium content less than 5 ppm).

Synthesis Example 1: Preparation of PUR Associative Thickener A1

Catalyst: 300 ppm K in the form of potassium acetate.

120.00 g of Pluriol® E6000 polyethylene glycol (BASF SE, molecular weight 6000 g / mol), 9.60 g Lutensol® TO10 (BASF SE), 11.10 g Lutensol® AT11 (11.10 g Lutensol® AT11 ( BASF SE) and 106 mg potassium acetate (i.e. 300 ppm potassium based on the total mixture) and then heated to a temperature of 100 ° C. By creating a vacuum of about 10 mbar for 6 hours, traces of water were removed until the final water content in the mixture was 230 ppm. At this point, the mixture was cooled to 80 ° C. By adding 5.88 g of hexamethylene diisocyanate, polymerization was started and the mixture was stirred at a temperature of 80 ° C. for 50 minutes until an isocyanate content of 0.0% was reached. The yellow colored precipitate was then dissolved in 586.3 g of water and the aqueous solution was mixed with 7.33 g of Euxyl® K701 (Schülke & Mayr), as well as 70 mg of 4-hydroxy-TEMPO stabilizer. The mixture was cooled to room temperature (25 ° C). Polymer A.1 was obtained (M _n = 11700 g / mol; M _w = 26900 g / mol) in the form of a clear, light yellow solution containing 20.8% solid. The viscosity of a 10% by weight aqueous solution of polyether polyurethane A.1 was 1550 mPa · s (shear rate 100 s ⁻¹ ) or 1360 mPa · s (shear rate 350 s ⁻¹ ).

Synthesis Example 2: Preparation of PUR Associative Thickener A.2

Catalyst: 600 ppm K in the form of potassium acetate.

120.00 g of Pluriol® E6000 polyethylene glycol, 9.60 g of Lutensol® TO10, 11.10 g of Lutensol® AT11, and 212 mg of potassium acetate (i.e. 600 ppm potassium calculated) were placed in a 2 liter polymerization reactor under nitrogen. total mixture) and then heated to a temperature of 100 ° C. By creating a vacuum of about 10 mbar, traces of water were removed for 5 hours until the final water content of the mixture was 225 ppm. At this point, the mixture was cooled to 80 ° C. By adding 5.88 g of hexamethylene diisocyanate, polymerization was started and the mixture was stirred at 80 ° C for 50 minutes until the isocyanate content of 0.0% was reached. The yellow colored precipitate was then dissolved in 586.3 g of water and the aqueous solution was mixed with 7.33 g of Euxyl® K701, as well as 70 mg of 4-hydroxy-TEMPO stabilizer. The mixture was cooled to room temperature (25 ° C). Polymer A.2 (M _n = 12,300 g / mol; M _w = 29,700 g / mol) was obtained in the form of a clear, light yellow solution containing 20.1% solid. The viscosity of a 10% by weight aqueous solution of polyether polyurethane A.2 was 3,700 mPa · s (shear rate 100 s ^-1 ) or 3,000 mPa · s (shear rate 350 s ^-1 ).

Synthesis Example 3: Preparation of PUR Associative Thickener A.3

Catalyst: 900 ppm K in the form of potassium acetate.

In a 2 liter polymerization reactor, 120.00 g of Pluriol® E6000 polyethylene glycol, 9.60 g of Lutensol® TO10, 11.10 g of Lutensol® AT11 and 318 mg of potassium acetate (i.e. 900 ppm potassium calculated total mixture) and then heated to a temperature of 100 ° C. By creating a vacuum of about 10 mbar for 4 hours, traces of water were removed until the final water content of the mixture was 242 ppm. At this point, the mixture was cooled to 80 ° C. The polymerization was started by adding 5.88 g of hexamethylene diisocyanate and the mixture was stirred at 80 ° C for 55 minutes until the isocyanate content reached 0.0%. The yellow colored precipitate was then dissolved in 586.3 g of water and the aqueous solution was mixed with 7.33 g of Euxyl® K701 preservative, as well as 70 mg of 4-hydroxy-TEMPO stabilizer. The mixture was cooled to room temperature (25 ° C). Polymer A.3 was obtained (M _n = 12700 g / mol; M _w = 33000 g / mol) in the form of a clear, light yellow solution containing 20.6% solids. The viscosity of a 10% by weight aqueous solution of A.3 polyether polyurethane was 6,000 mPa · s (shear rate of 100 s ⁻¹ ) or 4,400 mPa · s (shear rate of 350 s ⁻¹ ).

Synthesis Example 4: Preparation of PUR Associative Thickener A.4

Catalyst: 2000 ppm K in the form of potassium acetate.

90.00 g of Pluriol® E6000 polyethylene glycol, 7.20 g of Lutensol® TO10, 8.33 g of Lutensol® AT11 and 530 mg of potassium acetate (i.e. 2,000 ppm potassium calculated) were placed in a 2 liter polymerization reactor under nitrogen. total mixture) and then heated to a temperature of 100 ° C. By creating a vacuum of about 10 mbar for 5 hours, traces of water were removed until the final water content of the mixture was 210 ppm. At this point, the mixture was cooled to 80 ° C. By adding 4.41 g of hexamethylene diisocyanate, polymerization was started and the mixture was stirred at 80 ° C for 55 minutes until the isocyanate content of 0.0% was reached. The yellow colored precipitate was then dissolved in 439.7 g of water and the aqueous solution was mixed with 5.50 g of Euxyl® K701 preservative, as well as 50 mg of 4-hydroxy-TEMPO stabilizer. The mixture was cooled to room temperature (25 ° C). Polymer A.4 was obtained (M _n = 12,500 g / mol; M _w = 31,300 g / mol) in the form of a clear, light yellow solution containing 20.6% solids. The viscosity of a 10% by weight aqueous solution of simple polyether polyurethane A.4 was 5200 mPa · s (shear rate of 100 s ⁻¹ ) or 3800 mPa · s (shear rate of 350 s ⁻¹ ).

Synthesis Example 5: Preparation of PUR Associative Thickener A.4

Catalyst: 200 ppm K in the form of potassium acetate.

100.00 g polyethylene glycol (Merk KGaA, molecular weight 10,000 g / mol), 10.02 g 2-decyl-1-tetradecanol-20 EO and 55 mg potassium acetate (i.e. 200 ppm potassium based on total mixture) was placed under nitrogen in a polymerization reactor with a volume of 2 L and then heated to a temperature of 100 ° C. By creating a vacuum of about 10 mbar for 6 hours, traces of water were removed until the final water content in the mixture was 190 ppm. At this point, the mixture was cooled to 80 ° C. By adding 2.52 g of hexamethylene diisocyanate, polymerization was started and the mixture was stirred at 80 ° C. for 40 minutes until the isocyanate content of 0.0% was reached. The yellow colored precipitate was then dissolved in 450.2 g of water and the aqueous solution was mixed with 5.63 g of Euxyl® K701 preservative, as well as 60 mg of 4-hydroxy-TEMPO stabilizer. The mixture was cooled to room temperature (25 ° C). The obtained polymer A.5 (M _n = 19 100 g / mol; M _w = 48 500 g / mol) in the form of a clear, light yellow solution containing 20.7% solid. The viscosity of a 5% by weight aqueous solution of A.5 polyether polyurethane was more than 20,000 mPa · s (shear rate 100 s ^-1 ) or more than 20,000 mPa · s (shear rate 350 s ^-1 ).

Comparative example 1: Obtaining PUR-associative thickener A.6

No catalyst.

120.00 g of Pluriol® E6000 polyethylene glycol, 9.60 g of Lutensol® TO10 and 11.10 g of Lutensol® AT11 were placed under nitrogen in a 2 L polymerization reactor and then heated to a temperature of 100 ° C. By creating a vacuum of about 10 mbar for 5 hours traces of water were removed until the final water content in the mixture was 250 ppm. At this point, the mixture was cooled to 80 ° C. The addition of 5.88 g of hexamethylene diisocyanate started the polymerization and the mixture was stirred at 80 ° C for 32 hours until the isocyanate content of 0.0% was reached. Then, the yellow colored precipitate was dissolved in 586.3 g of water and the aqueous solution was mixed with 7.33 g of Euxyl® K701 preservative, as well as 70 mg of 4-hydroxy-TEMPO stabilizer. The mixture was cooled to room temperature (25 ° C). Polymer A.6 (M _n = 10,000 g / mol; M _w = 23,200 g / mol) was obtained in the form of a clear, light yellow solution containing 18.8% solids. The viscosity of a 10 wt.% Aqueous solution of A.6 polyether polyurethane was more than 100 mPa · s (shear rate of 100 s ⁻¹ ) or more than 100 mPa · s (shear rate of 350 s ⁻¹ ).

Comparative example 2: Obtaining PUR-associative thickener A.6

No catalyst.

100.00 g of polyethylene glycol (Merk KGaA, molecular weight 10,000 g / mol) and 10.02 g of 2-decyl-1-tetradecanol-20 EO were placed under nitrogen in a 2 L polymerization reactor and then heated to a temperature of 100 ° C. By creating a vacuum of about 10 mbar for 6 hours, traces of water were removed until the final water content of the mixture was 185 ppm. At this point, the mixture was cooled to 80 ° C. By adding 2.52 g of hexamethylene diisocyanate, polymerization was started and the mixture was stirred at 80 ° C for 12 hours until the isocyanate content of 0.0% was reached. Then, the yellow colored precipitate was dissolved in 450.2 g of water and the aqueous solution was mixed with 5.63 g of Euxyl® K701 preservative, as well as 60 mg of 4-hydroxy-TEMPO stabilizer. The mixture was cooled to room temperature (25 ° C). The obtained polymer A.7 (M _n = 5200 g / mol; M _w = 14500 g / mol) in the form of a clear, light yellow solution containing 18.5% solids. The viscosity of a 10% by weight aqueous solution of A.7 polyether polyurethane was <100 mPa · s (shear rate 100 s ^-1 ) or <100 mPa · s (shear rate 350 s ^-1 ).

Comparative example 3: Obtaining PUR-associative thickener A.8

Catalyst: dibutyltin dilaurate.

90.00 g of Pluriol® E6000 polyethylene glycol, 7.20 g of Lutensol® TO10, 8.33 g of Lutensol® AT11 and 144 mg of dibutyltin dilaurate (DBTL) (i.e. 300 ppm of tin per total mixture) were placed under nitrogen in nitrogen 2 liter polymerization reactor and then heated to a temperature of 100 ° C. By creating a vacuum of about 10 mbar, traces of water were removed for 5 hours until the final water content of the mixture was 250 ppm. At this point, the mixture was cooled to 80 ° C. By adding 4.41 g of hexamethylene diisocyanate, polymerization was started and the mixture was stirred at 80 ° C for 60 minutes until the isocyanate content of 0.0% was reached. The yellow colored precipitate was then dissolved in 440.3 g of water and the aqueous solution was mixed with 5.50 g of Euxyl® K701 preservative, as well as 60 mg of 4-hydroxy-TEMPO stabilizer. The mixture was cooled to room temperature (25 ° C). The obtained polymer A.8 (M _n = 10100 g / mol; M _w = 22000 g / mol) in the form of a clear, light yellow solution containing 20.4% solid. The viscosity of a 10% by weight aqueous solution of A.8 polyether polyurethane was 720 mPa · s (shear rate of 100 s ⁻¹ ) or 660 mPa · s (shear rate of 350 s ⁻¹ ).

Comparative example 4: Obtaining PUR-associative thickener A.9

Catalyst: 1,4-diazabicyclo [2.2.2] octane (DABCO).

120.00 g of Pluriol® E6000 polyethylene glycol, 9.60 g of Lutensol® TO10, 11.10 g of Lutensol® AT11 and 36 mg of 1,4-diazabicyclo [2.2.2] octane (DABCO; 300 ppm based on total mixture) was placed under nitrogen in a 2 liter polymerization reactor and then heated to a temperature of 100 ° C. By creating a vacuum of about 10 mbar for 5 hours, traces of water were removed until the final water content of the mixture was 230 ppm. At this point, the mixture was cooled to 80 ° C. By adding 5.88 g of hexamethylene diisocyanate, polymerization was started and the mixture was stirred at 80 ° C for 13 hours until the isocyanate content of 0.0% was reached. The yellow colored precipitate was then dissolved in 586.5 g of water and the aqueous solution was mixed with 7.33 g of Euxyl® K701 preservative, as well as 70 mg of 4-hydroxy-TEMPO stabilizer. The mixture was cooled to room temperature (25 ° C). The obtained polymer A.9 (M _n = 8 500 g / mol; M _w = 17400 g / mol) in the form of a clear, light yellow solution containing 18.7% solids. The viscosity of a 10% by weight aqueous solution of A.9 polyether polyurethane was 105 mPa · s (shear rate 100 s ⁻¹ ) or 105 mPa · s (shear rate 350 s ⁻¹ ).

Example composition 1:

Cremophor® A6 / Cremophor® A25 Cosmetic Formulations

The following cosmetic formulations were prepared by adding aqueous phase B to oil phase A, followed by mixing the resulting oil-in-water emulsion (O / W) with a preservative (phase C). The following formulations were prepared based on Cremophor® A6 / Cremophor® A25.

Table 1 Cremophor® A6 / Cremophor® A25 Compositions Phases Ingredients F.1.1 F.1.2 F.1.3 F.1.4 F.1.6 F.1.8 Phase A Cremophor®A6 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Cremophor®A25 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Lanette®O 2.5 g 2.5 g 2.5 g 2.5 g 2.5 g 2.5 g Paraffin oil 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g Luvitol®EHO 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g Phase B PUR thickener A.1 A.2 A.3 A.4 A.6 A.8 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 1,2-propylene glycol 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g Water 77.5 g 77.5 g 77.5 g 77.5 g 77.5 g 77.5 g Phase C Euxyl®K300 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g

Example composition 2:

Stearate ester cosmetic formulations

The following cosmetic formulations were prepared by adding aqueous phase B to oil phase A, followed by mixing the resulting oil-in-water emulsion (O / W) with a preservative (phase C). The following formulations were prepared based on stearate ester.

table 2 Stearate Ether Formulations Phases Ingredients F.2.1 F.2.2 F.2.3 F.2.4 F.2.6 F.2.8 Phase A Cutina®GMS 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Lanette®18 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Dow Corning 345 Liquid 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g Cetiol® oe 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g 3.0 g Abil®350 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Dry flo pc 1.0 g 1.0 g 1.0 g 1.0 g 1.0 g 1.0 g Myrj 52 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g 2.0 g Phase B PUR thickener A.1 A.2 A.3 A.4 A.6 A.8 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g Glycerol 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g 5.0 g Water 79.0 g 79.0 g 79.0 g 79.0 g 79.0 g 79.0 g Phase C Euxyl®K300 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g 0.5 g

Viscosity of cosmetic formulations from F.1.1 to F.1.8 depending on salt concentration.

Table 3 Structure Viscosity [MPa · s] with the addition of 2.0% NaCl F.1.1 12100 F.1.2 17100 F.1.3 26200 F.1.4 17000 F.1.6 6800 F.1.8 11400

Viscosity of cosmetic formulations from F.2.1 to F.2.8 depending on salt concentration.

Table 4 Structure Viscosity [MPa · s] with the addition of 2.0% NaCl F.2.1 16700 F.2.2 21800 F.2.3 21200 F.2.4 18100 F.2.6 10,000 F.2.8 14700

Viscosity of polyurethanes from A.1 to A.9 depending on shear rate and concentration.

Table 5. Polymer The concentration of polymer in water [wt.%] Viscosity [MPa · s] Shear rate 100 1 / s Shear rate 350 1 / s A.1 10 1550 1360 A.2 10 3700 3000 A.3 10 6000 4400 A.4 10 5200 3800 A.5 5 > 20,000 > 20,000 A.6 10 one hundred one hundred A.7 10 <100 <100 A.8 10 720 660 A.9 10 105 105

Figure 1. GPC chromatogram of polyurethanes A.5 and A.7

Examples of using

Reference is hereby made in full to examples of technical use published in international patent application WO 2009/135857 on pages 87 to 114.

The polyurethanes PU.1 to PU.11 used in the examples in this publication are replaced for the purposes of this invention by the polyurethanes A.1, A.2, A.3, A.4 or A.5 of the present invention, resulting in a similar appropriate cosmetic formulations obtained.

Other typical formulations of the invention are described hereinafter, without however limiting the invention to these examples.

In addition to the preparation of cosmetic compositions described herein, polyurethanes A.1, A.2, A.3, A can also be added to the emulsion formed after purification from the aqueous or oil phase at 60-80 ° C or to the cooled emulsion at a temperature of about 40 ° C .4 or A.5, as well as combinations thereof.

The object of the invention is the subsequent addition to the cosmetic composition obtained according to the invention of polyurethanes in order to establish the desired viscosity.

Unless otherwise explicitly described, the percentage data are mass percent data.

Oil-in-Water Emulsion (O / W)

Phase Ingredient / INCI F.3.1 F.3.2 F.3.3 F.3.4 F.3.5 A Water up to 100 up to 100 up to 100 up to 100 up to 100 Glycerol 3.0 5.50 4,50 5.00 3,5 PUR thickener A.1 3.0 1,5 0.8 2.0 2.5 Copolymer of hydroxyethyl acrylate and sodium acryloyl dimethyl taurate, squalane, Polysorbate 60 1,0 0.5 B Glycerol Citrate Stearate 1.80 2.00 3.00 1,50 2 Sucrose stearate 1.00 1.20 2.00 2.20 1,5 Cetearyl alcohol 1.80 2.00 1,50 2.40 2,8 Ethylhexyl palmitate 6.00 5.00 3,50 3.00 5.5 Caprylic / Capric Acid Triglycerides 5.00 5.00 1.00 2.00 3,5 Octyldodecanol 1,50 3.00 2.40 5,0 4.6 Dimethicone 0.20 0.50 2.00 1.80 1.4 C Ammonium Acryloyl Dimethyl Taurate / VP Copolymer 0.5 0.1 Carbomer 0.05 0.1 D Sodium hydroxide 0.02 0.04 E Bisabolol 0.5 0.3 0.20 0.35 1,0 Phenoxyethanol, paraben mixture 1.00 0.60 0.70 0.60 0.5 Perfume 0.05 0.10 0.10 0.05 0.05

Getting

The separated phases A and B are heated to a temperature of about 80 ° C. Phase C is mixed into phase B, and then phase A is mixed into phase B / C and briefly homogenized.

Phase D is added (if necessary) and, after stirring, cooled to a temperature of about 40 ° C. The components of phase E are successively added to the emulsion and, after stirring, cooled to room temperature. Homogenize for a short time.

Instead of an oil-in-water emulsion (O / W) containing an A.1 polyurethane thickener, an oil-in-water emulsion (O / W) containing one or more of A.2 polyurethanes is also obtained, A.3, A.4 or A.5.

Hydrodispersion Phase Ingredients / INCI F.4.1 F.4.2 F.4.3 F.4.4 F.4.5 A Stearyl alcohol 0.5 1,5 2.0 Cetyl alcohol 1.00 2.5 C12-15 alkyl benzoate 2.5 4.0 Dicapril ether 4.0 6.0 Dicaprilat / Dicaprat Butylene 4.0 2.0 1,0 Dicapryl carbonate 2.0 3.0 4.0 Cyclopentasiloxane, cyclohex-sasiloxane 2.0 0.5 Sweet Almond Oil 2.0 0.5 Shea Butter 2.0 1,0 Hydrogenated Polyisobutene 3.0 1,0 7.0 0.5 2.0 Squalane 2.0 0.5 Vitamin E Acetate 0.50 0.25 1.00 B Mixed polymer acrylate / C10-30 alkyl acrylate 0.3 0.1 0.2 0.15 0.2 C Water up to 100 up to 100 up to 100 up to 100 up to 100 Polyacrylamide, C13-14 Isopha-Rafine, Laureth-7 1,0 1,5 0.75 PUR thickener A.1 2.5 2.0 0.9 1,5 3.0 Propylene glycol 3.00 5,0 2.5 7.50 10.0 D Sodium hydroxide 0.12 0.04 0.08 0.06 0.08 E Niacinamide 0.30 3.0 1,5 0.5 0.20 Water 2.0 10.0 5,0 2.0 " 2.0 F DMDM hydantoin 0.60 0.45 0.25 Methylparaben 0.50 0.25 0.15 Phenoxyethanol 0.50 0.40 1.00 Ethylhexylglycerol 1.00 0.80 Ethanol 3.00 2.00 1,50 7.00 G Flavoring 0.20 0.05 0.40

Receiving:

Phases A and C are separately heated to a temperature of about 80 ° C.

Phase B is mixed into phase A, and then phase C is mixed into phase A / B. Not homogenized for long. Phase D is added and cooled to a temperature of about 40 ° C. with stirring. Phase E is added and cooled to a temperature of about 30 ° C. Phases F and G are added to the emulsion and cooled to room temperature with stirring. Homogenize for a long time.

Instead of hydrodispersion containing thickener A.1, hydrodispersions are also obtained containing one or more of the polyurethanes A.2, A.3, A.4 or A.5.

Stable solid emulsions. Phase Ingredient / INCI F.5.1 F.5.2 F.5.3 F.5.4 F.5.5 A Mineral oil 4.0 6.0 16,0 10.0 6.0 Octyldodecanol 9.0 9.0 5,0 Ethylhexylisononanoate 9.0 9.0 6.0 5,0 8.0 Isohexadecane 9.0 5,0 4.0 8.0 Dimethicone 0.5 2.0 1,0 1,5 Cera Microcristallina, paraffin liquid 0.35 0.75 3.0 Phenyltrimethicone 2.0 1,0 2.5 3.0 Silica 2.5 6.0 2.5 Aluminum Starch Octenylsuccinate 2.0 1,0 0.5 Tapioca starch 0.5 B Titanium dioxide coated 1,0 0.5 3.0 2.0 4.0 Zinc oxide 5,0 10.0 2.0 3.0 C Ammonium Acryloyldimethyl Taurate / Beheneth-25 Methacrylate Crosslinked Polymer 0.2 1,0 0.5 D Water up to 100 up to 100 up to 100 up to 100 up to 100 Hydroxypropyl methylcellulose 0.1 0.05 Sorbitol 5,0 7.0 8.5 3.0 4,5 PUR thickener A.1 3.0 5,0 0.9 1.4 2.0 E Mixed parabens 0.3 0.6 0.2 0.4 Phenoxyethanol 0.2 0.3 0.4 0.5 0.4 Diisolidinyl Urea 0.23 0.2 F Flavoring 0.2 0.3 0.1

Receiving:

Phase A is heated to 80 ° C.

Phase B is added to phase A and homogenized for 3 minutes, phase C is mixed.

Cellulose (if necessary) is first allowed to swell in water, then the remaining phase D ingredients are added and heated to 80 ° C.

Phase D is mixed with phase A + B + C and homogenized. The emulsion is cooled to a temperature of about 40 ° C. and phases E and F are added. Cool to room temperature with stirring and homogenize.

Instead of a stabilized emulsion containing A.1 polyurethane thickener, stabilized emulsions are also prepared containing one or more of A.2, A.3, A.4 or A.5 polyurethanes.

Sunscreen Phase Ingredient / INCI F.6.1 F.6.2 F.6.3 F.6.4 F.6.5 A Water up to 100 up to 100 up to 100 up to 100 up to 100 Disodium Ethylenediaminetetra-Acetic Acid EDTA 0.1 0.1 0.1 0.1 0.1 Glycerol 3.00 7.50 8.0 7.50 5.00 Benzophenone-4 2.0 4.0 Phenylbenzimidazole sulfonic acid 0.50 4.00 8.0 Triethanolamine 1,0 0.25 2.0 2.0 4.0 Panthenol 0.5 0.75 1,0 PUR thickener A.1 2.5 g 0.5 g 2.0 g 4.0 1,5 Xanthan gum 0.3 0.15 0.2 B Octocrylene 8.0 7.5 Ethylhexylmethoxycinnamate, diethylaminohydroxybenzoyl hexylbenzoate 5,0 10.0 8.0 3.0 7.0 Steareth-21 2.0 3.0 2.5 Steareth-2 1,5 PEG-40 stearate 1,0 2.0 Glycerin monostearate SE 1,0 3.0 1,5 1,5 Dibutyl adipate 3.0 5,0 3,5 2.5 2.0 Cetearyl alcohol 2.0 0.5 3.0 Stearyl alcohol 1,5 3.0 2.5 0.6 2.0 Butyrospermum Parkii (Shea Butter) 1,0 0.5 1,0 1,5 Dimethicone 1,0 0.5 1,5 0.8 2.0 PVP hexadecene copolymer 0.20 0.50 0.8 1.00 Bisabolol 0.2 0.1 0.3 C DMDM hydantoin 0.5 0.5 0.5 0.5 0.75 Water, aloe leaf juice Baroadensis 0.5 1,0 Alpha glucosylrutin 0.60 0.5 0.4 0.25 0.3 Flavoring 0.10 0.25 0.30 0.40 0.20

Receiving:

Phases A and B are separately heated to a temperature of about 80 ° C.

Mix phase A to phase B and briefly homogenize.

Cool with stirring to a temperature of about 40 ° C. The components of phase C are successively added to the emulsion and cooled to room temperature with stirring. Homogenize for a short time.

Instead of sunscreen containing A.1 polyurethane thickener, sunscreens containing one or more of A.2, A.3, A.4 or A.5 polyurethanes are also prepared.

Face cream with sodium ascorbyl phosphate Phase Ingredient / INCI F.7.1 F.7.2 F.7.3 F.7.4 F.7.5 A Water up to 100 up to 100 up to 100 up to 100 up to 100 Butylene glycol 5,0 6.5 5.5 3,5 4.0 PUR thickener A.1 3,5 1,5 2.5 5,0 2.0 Xanthan gum 0.25 0.2 0.1 Potassium sorbate 0.1 0.1 0.1 0.1 0.1 Imidazolidinyl urea 0.3 0.2 B Potassium Cetyl Phosphate 1,5 2.0 1.9 2.5 1,0 Caprylic / Capric Acid Triglycerides 2.0 5,0 3.0 4.0 2.5 Stearyl alcohol 0.5 1,5 2.0 1,0 3.0 Cetearyl Alcohol, Diethyl Phosphate, Ceteth-10 Phosphate 1,5 2.0 1.8 1.9 2.1 Simmondsia Chinensis Seed Oil (Jojoba) 3.0 1,5 0.5 1,0 2.5 Mineral oil 2.0 5,0 10.0 7.5 4.0 Paraben mixture 0.2 0.2 0.2 0.2 0.2 C Sodium ascorbyl phosphate 5,0 2.0 3.0 4.0 1,5 Lactic acid q.s. q.s. q.s. q.s. q.s. Water 10.0 4.0 5,0 10.0 3.0 D Tocopherol 0.1 0.2 Retinol 0,03 0,025 0.05 E Flavoring 0.1 0.05 0.05 0.1 0.15

Receiving:

Phases A and B are separately heated to a temperature of about 80 ° C.

Phase A is mixed into phase B and briefly homogenized.

Phase C is mixed into phase A + B and homogenized.

Cool with stirring to a temperature of about 40 ° C. The pH of phase C is adjusted to less than 6.5 with lactic acid. Phase C is added and cooled with stirring to a temperature of about 30 ° C. Phase D and E are added. Cool with stirring to room temperature and homogenize briefly.

Note: the pH of the emulsion is adjusted with lactic acid to <6.5.

Instead of a face cream containing A.1 polyurethane thickener, face creams containing one or more of A.2, A.3, A.4 or A.5 polyurethanes are also prepared.

Hydroxycarboxylic Acid Creams Phase Ingredient / INCI F.8.1 F.8.2 F.8.3 A Ceteareth-6, stearyl alcohol 2.0 2.5 Ceteareth-25 2.0 2.5 PEG-100 stearate, glycerol stearate 3,5 0.5 Poly glycery 1-3 distearate 2.0 Mineral oil 8.0 3,5 5,0 Cetearylethylhexanoate 7.0 5.5 4.0 Sorbitan stearate 0.5 1,5 0.5 Cera Alba (Beeswax) 0.5 1,0 Cetyl alcohol 1,5 3,5 4.0 Dimethicone 0.2 2.0 0.5 B Panthenol 1,0 0.5 0.3 Propylene glycol 3.0 2.0 5,0 PUR thickener A.1 1,0 3.0 5,0 Hydroxy Acid 3.0 7.0 10.0 Water up to 100 up to 100 up to 100 C Sodium hydroxide q.s. q.s. q.s. D Bisabolol 0.2 0.1 0.3 Preservative q.s. q.s. q.s. Flavoring q.s. q.s. q.s. Note: Alpha hydroxy acid: lactic acid, citric acid, malic acid, glycolic acid. Dihydroxy acid: tartaric acid. Beta hydroxy acid: salicylic acid.

PH> 3

Receiving:

The separated phases A and B are heated to a temperature of about 80 ° C. The pH of phase B is adjusted, if necessary, with sodium hydroxide to a value> 3. Phase B is mixed into phase A, briefly homogenized.

Cool with stirring to a temperature of about 40 ° C, phase D components are added sequentially, homogenize again.

Instead of a hydroxycarboxylic acid cream containing a polyurethane thickener A.1, hydroxycarboxylic acid creams containing one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also obtained.

Emulsion with deodorant Phase Ingredient / INCI F.9.1 F.9.2 F.9.3 F.9.4 F.9.5 Ceteareth-6, stearic alcohol 1,5 2.0 1,0 Ceteareth-25 1,5 0.5 1,0 PEG-40 hydrogenated castor oil 0.5 1,0 2.0 Glycerol stearate 0.5 2.0 1,0 Cetyl alcohol 2.0 1,0 0.5 2.5 0.2 Hydrogenated Cocoglycerides 2.0 1,0 0.5 Hydrogenated Poly-Isobutylene 10.0 20,0 5,0 3.0 Decyl oleate 3.0 2.0 8.0 5,0 Bis-PEG / PPG-14/14 dimethicone, cyclopentasiloxane 3.0 3,5 4.0 2.0 1,5 Talc 3.0 2.5 1,5 Magnesium and aluminum silicate 1,0 0.5 1,0 1,5 B Propylene glycol 10.0 5,0 7.5 20,0 15.0 PUR thickener A.1 0.5 1,0 3.0 3,5 2.0 Xanthan gum 0.2 0.1 0.05 Cetyl hydroxyethyl cellulose 0.3 0.1 Aluminum Hydrochloride 5,0 10.0 20,0 Aluminum zirconium tetrachlorohydrex GLY 15.0 50,0 20,0 Water up to 100 up to 100 up to 100 up to 100 up to 100 C Catalytic converter q.s. q.s. q.s. q.s. q.s. D Alcohol 5,0 10.0 25.0 7.5 6.0 Allantoin 0.1 0.1 0.1 0.1 0.1 Preservative q.s. q.s. q.s. q.s. q.s. Flavoring q.s. q.s. q.s. q.s. q.s.

Receiving:

Phases A and B are separately heated to a temperature of about 80 ° C.

During homogenization, phase B is mixed into phase A. If necessary, adjust the pH through phase C to 4-5. Cool to a temperature of about 40 ° C. Phase D is added and cooled with stirring to room temperature. Shortly homogenize.

Note: the pH of the emulsion is adjusted to 4-5.

Instead of an emulsion with a deodorant containing a polyurethane thickener A.1, emulsions with a deodorant containing one or more of the polyurethanes A.2, A.3, A.4 or A.5 are also obtained.

Hair removal cream Phase Ingredient / INCI F.10.1 F.10.2 F.10.3 A Glycerol stearate 1,0 Ceteareth-12 1,0 2.0 Ceteareth-20 1,0 2.0 Stearyl alcohol 4.0 1,0 Cetyl alcohol 4.0 1,0 Mineral oil 6.0 4.0 Apricot kernel oil Prunus Armeniaca 3.0 1,0 2.0 B Propylene glycol 1,0 2.0 10.0 Calcium carbonate 10.0 Calcium hydroxide 7.0 Sodium hydroxide 0.4 0.6 Calcium thioglycolate 5,0 3.0 5,0 PUR thickener A.1 3.0 1,5 2.0 Water up to 100 up to 100 up to 100 C Tocopherol I 0.1 0.2 0.15 Bisabolol 0.2 0.1 0.3 Flavoring q.s. q.s. q.s.

Receiving:

Phases A and B are separately heated to a temperature of about 80 ° C.

Phase B is mixed into phase A, briefly homogenized. It is cooled to a temperature of about 40 ° C, phase C is added, it is cooled with stirring to room temperature and homogenized again.

Note: the pH of the emulsion is adjusted to a value of> 10.

Instead of a hair removal cream containing A.1 polyurethane thickener, hair removal creams containing one or more of A.2, A.3, A.4 or A.5 polyurethanes are also prepared.

Emulsion for tanning Phase Ingredient / INCI F.11.1 F.11.2 F.11.3 F.11.4 A Isohexadecane 4.0 2.0 3.0 1,0 Dimethicone 1,0 1,0 0.5 1,5 Ethanol 2.0 2.5 1,5 2.5 Isopropyl myristate 1,0 2.0 3.0 Simmondsia Chinensis Seed Oil (Jojoba) 2.0 1,0 0.5 0.5 Polyglyceryl-3 Methylglucose Distearate 3.0 3,5 PEG-40 stearate 2.5 2.0 Lecithin 0.5 1,0 Cetearyl glucoside 0.5 0.5 Sorbitan oleate 0.5 0.5 0.3 B Glycerol 4.0 5,0 butylene glycol 4.0 3.0 PUR thickener A.1 1,0 3.0 1,5 2.5 Xanthan gum 0.1 0.1 Water up to 100 up to 100 up to 100 up to 100 C Dihydroxyacetone 1,5 5,0 Erythrulose 2.0 4.0 Water 5,0 10.0 5,0 8.0 Lemon acid q.s. q.s. q.s. q.s. D Bisabolol 0.3 0.5 0.2 0.4 Tocopheryl acetate 0.7 0.5 0.6 1,0 Preservative q.s. q.s. q.s. q.s. Flavoring q.s. q.s. q.s. q.s.

Receiving:

Phases A and B are separately heated to a temperature of about 80 ° C.

Phase B is mixed into phase A, briefly homogenized.

Cool with stirring to a temperature of about 40 ° C, add phase C and cool with stirring to a temperature of about 30 ° C. The components of phase D are added sequentially and, with stirring, cooled to room temperature, briefly homogenized.

Note: the pH of the emulsion is adjusted to a value of 4-5.5.

Instead of a tan emulsion containing A.1 polyurethane thickener, emulsions for containing one or more of A.2, A.3, A.4 or A.5 polyurethanes are also obtained.

Conditioning shampoo (moisturizing). Ingredient / INCI F.12.1 F.12.2 F.12.3 F.12.4 Water up to 100 up to 100 up to 100 up to 100 Sodium Lauryl Sulfate 35.7 30,0 12.0 Cocoamidopropyl Betaine 13.5 15.0 Disodium cocoamphodiacetate 10.0 Sodium Cocoamphoacetate 6.0 Polysorbate 20 5,0 Dicetyl glucoside 5,0 1,5 Laureth-3 2.0 Sodium Lauryl Sulfate, Gly-Coldstearate, Cocamide MEA, Laureth-10 3.0 2.0 Cocoglucoside, glycerol oleate 5,0 Dimethicone 2.0 Polymer air conditioning 2.0 0.5 0.75 0.4 PUR thickener A.1 0.75 1,2 0.5 1,0 PEG-150 distearate 3.0 Lemon acid q.s. q.s. Preservative q.s. q.s. q.s. q.s. Flavoring q.s. q.s. q.s. q.s. Dye q.s. q.s. q.s. q.s. Sodium chloride 1,0 1,0

By conditioning polymer is meant Polyquaternium-7, PQ-10, PQ-16, PQ-39, PQ-44, PQ-46, PQ-67, guar hydroxypropyltriammonium chloride, PQ-87, as well as a combination thereof.

Instead of conditioner shampoo containing A.1 polyurethane thickener, conditioner shampoos also contain one or more of A.2, A.3, A.4 or A.5 polyurethanes.

Hair conditioner. Phase Ingredient / INCI F.13.1 F.13.2 F.13.3 F.13.4 F.13.5 A Water up to 100 up to 100 up to 100 up to 100 up to 100 PUR thickener A.1 2.5 1,5 3.0 0.6 2.0 Hydroxyethyl cellulose 0.05 0.1 0.2 Propylene glycol 1,0 2.0 0.8 0.5 Panthenol 0.5 0.75 0.25 0.3 B Quaternium-91, Cetaric Alcohol, Cetrimonium Methosulfate 2.0 1,5 Distearoethylhydroxyethylammonium methosulfate, cetearyl alcohol 3.0 4.0 Hydrogenated Polyisobutene 1,0 1,5 1,0 Cyclopentasiloxane 2.0 1,0 0.5 Isopropyl palmitate 1,0 2.0 Persea Gratissima Oil (Avacodo) 2.5 Steareth-2 0.75 0.5 Ceteareth-6, stearyl alcohol 1,5 0.5 Ceteareth-25 1,5 Cetearyl alcohol 2.0 1,5 0.5 4.0 C Acrylate / C 10-30 Alkyl Acrylate Copolymer 0.1 0.2 0.15 D Cetrimonium chloride 1,5 3.0 Polymer air conditioning 2.0 6.0 3.0 1,5 0.8 E Preservative q.s. q.s. q.s. q.s. q.s. Flavoring q.s. q.s. q.s. q.s. q.s.

By conditioning polymer is meant Polyquaternium-7, PQ-10, PQ-16, PQ-39, PQ-44, PQ-46, PQ-67, Guarhydroxypropyltrimonium Chloride, PQ-87, as well as a combination thereof.

Receiving:

Phases A and B are separately heated to a temperature of about 80 ° C.

Phase C is mixed into phase B, then phase B / C is mixed into phase A and briefly homogenized.

Cool with stirring to a temperature of about 50 ° C, phase D components are added sequentially and cool with stirring to a temperature of about 30 ° C. The components of phase E are added sequentially and cooled to room temperature with stirring. Shortly homogenize.

Instead of a hair conditioner containing A.1 polyurethane thickener, hair conditioners containing one or more of A.2, A.3, A.4, or A.5 polyurethanes are also prepared.

Claims (14)

1. The method of producing polyurethanes containing:
I) at least two hydrophilic site S,
II) at least one hydrophilic site P, different from S,
III) at least two terminal hydrophobic section T,
IV) at least two hydrophobic sites D, different from T, and
a) each section T is directly connected to section S,
b) at least one section D is attached to each section S at least on one side,
c) at least two sites D are attached to each site P, characterized in that the process is carried out in the presence of at least one alkali or alkaline earth metal salt of a monocarboxylic acid of the general formula R-COOH, in which R is a hydrocarbon residue with 1-12 atoms carbon. 2. The method according to claim 1, wherein at least a portion of the polyurethanes contains allophanate segments. 3. The method according to claim 1, wherein at least a portion of the polyurethanes contains isocyanurate segments. 4. The method according to p. 1, characterized in that, based on the reaction mixture, the number of solvents that differ from compounds introducing hydrophilic and hydrophobic sites into polyurethanes ranges from 0 to 10 wt.%. 5. The method according to p. 1, characterized in that the process is carried out in one stage. 6. The method according to p. 1, characterized in that it additionally also receive polyurethanes, which:
I) contain at least two hydrophilic site S,
II) do not contain a hydrophilic site P,
III) contain at least two terminal hydrophobic section T,
Iv) contain at least one hydrophobic site D, different from T,
moreover
a) each section T is directly connected to section S,
b) a plot D is attached to each section S 7. The method according to p. 1, characterized in that at least one hydrophilic region P has a number average molecular weight of from 4000 to 12000 g / mol. 8. The method according to p. 1, characterized in that the process is carried out in the presence of at least one potassium acetate. 9. The method according to p. 1, characterized in that the process is carried out in the presence of less than 10 ppm. tin. 10. The method according to p. 1, characterized in that the process is carried out in the presence of less than 10 ppm. zinc. 11. The method according to one of paragraphs. 1-10, characterized in that to obtain polyurethanes, in each case, use at least
- one alkoxylated alcohol with 4-30 carbon atoms,
- one simple polyetherdiol and
- one diisocyanate. 12. The method according to p. 11, characterized in that
- at least one alcohol with 4-30 carbon atoms is a branched alcohol with 12-30 carbon atoms,
- at least one simple polyetherdiol has a number average molecular weight M _n ranging from 4000 to 12000 g / mol and
- at least one diisocyanate is an aliphatic diisocyanate. 13. The use of polyurethanes obtained by the method according to PP. 1-12, as a thickener in aqueous formulations. 14. A composition containing at least one polyurethane obtained by the method according to PP. 1-12.

Images