KR20140001825A - Associative thickener for aqueous preparations - Google Patents

Abstract

The present invention relates to association thickeners based on compounds comprising at least one hydrophobically modified polyether dendron as end group.

Description

Associative thickener for aqueous formulations {ASSOCIATIVE THICKENER FOR AQUEOUS PREPARATIONS}

The present invention relates to association thickeners based on compounds comprising at least one hydrophobically modified polyether dendron as end group.

Thickeners with associative effects, as well as cellulose ether and acrylate thickeners, cited as the most common pseudoplastic thickeners for aqueous systems, also play an important part.

In its structural configuration, the association thickeners are compounds with distinct hydrophilic and hydrophobic sections, which, due to their fractionated structure, can form some stable association with themselves and / or with the coating components (binders, pigments, fillers, etc.). have. It is possible, mainly by changes in chemical structure, to change the stability of the association and the rheological properties of the coating system.

The most well-known is the associative thickener is a polyurethane-based polymer, it referred to as the HEUR thickener ( "nonionic h ydrophobically modified e thylene oxide ur ethane block copolymer").

The HEUR-type associative thickeners described in US Pat. No. 4,079,028 (Rohm & Haas) in the late 1970s consist of linear and / or branched polyethylene glycol blocks and hydrophobic sections, which are generally connected to one another via urethane groups.

The thickening effect of conventional HEUR thickeners stems from the fact that the hydrophilic polyethylene glycol moiety constitutes a three-dimensional molecular assembly that ensures compatibility with water and that the hydrophobic moiety provides viscosity through association.

EP 761780 and EP 1111014 (Asahi Denka) disclose polyurethane thickeners which consist of polyethylene glycol as internal hydrophilic units, linear diisocyanates as internal hydrophobic units and alkyl-chain-branched alcohols ethoxylated as hydrophilic-hydrophobic chain ends. have.

Associative thickeners are used in a variety of fields, including the growing field of cosmetics.

EP 1584331 and EP 1013264 (Shiseido) describe the use of the polyurethanes described in EP # 761780 described above primarily as thickeners for cosmetic preparations.

WO 2006/002813 (Cognis) describes polyurethane thickeners for various applications in aqueous media. Thickeners include hydrophilic polyols having two or more hydroxyl groups, one or more hydrophobic compounds such as long chain alcohols such as and at least bifunctional isocyanates. Excess NO groups form branches in the chain. Such polyurethanes are used, for example, in cosmetic preparations.

WO 02/88212 (Cognis) describes polyurethanes formed from ethoxylated long chain alcohols and cyclic diisocyanate oligomers, for example isocyanurates, and describes their use in cosmetics.

EP 725097 (Bayer) describes polyurethane thickeners prepared by reacting polyethers prepared by alkoxylation of alcohols or alkylphenols with polyisocyanates, and the ratio of NCO to OH equivalents is 0.9: 1 to 1.2: 1. Range. Such thickeners have been proposed for use in, for example, aqueous emulsion paints.

WO 2009/135856 and WO 2009/135857 describe polyurethanes having substantially linear backbones which can be dispersed in water and consist of repeating hydrophilic and hydrophobic moieties, for example the use of such polyurethanes in cosmetics It is described.

DE 102008030992 relates to linear-dendrimeric polyglycerol compounds, methods for their preparation and their use for solubilizing hydrophobic substances, more particularly as carriers or transport systems for active compounds and / or signal compounds.

It is an object of the present invention to provide a thickener suitable for cosmetic preparations and having defined properties. Examples of preferred properties of such thickeners include the following:

Particularly effective and stable thickening effects when using high levels of electrolytes and other components in the formulation, such as pigments;

-Above room temperature-stable thickening effect, for example at a temperature below 40 ° C;

Stable thickening effect over a very wide pH range, for example from pH 2 to pH 13;

Compatibility with conventional ingredients of cosmetic preparations;

Ease of incorporation into cosmetic preparations;

Substantial absence of ingredients that are unsuitable for cosmetics, such as toxic heavy metals.

The above-mentioned object was achieved through the provision of compounds having end groups based on polyether dendrons.

The present invention therefore provides compounds comprising at least one group of formula (I):

[Wherein, the definition is as follows:

R ¹ : independently in each occurrence C ₄ -C ₄₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₃₀ -aryl, C ₇ -C ₄₀ -aralkyl, C ₇ -C ₄₀ -alkylaryl Or-(R ² -O) _n -R ³ ,

R ² , R ⁴ : in each occurrence independently is C ₂ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, or C ₇ -C ₁₀ -aralkylene;

R ³ : H, C ₁ -C ₄₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₃₀ -aryl, C ₇ -C ₄₀ -aralkyl or C ₇ -C ₄₀ -alkylaryl;

n: 1 to 200;

m: 1 to 6;

p: 0 to 200;

: 화합물의 잔부에의 말단기의 연결이고;

: Linkage of end groups to the remainder of the compound;

With the proviso that when p = 0, the end groups are also NR rather than through O⁵ (R⁵ Are H and C_One-C₃₀May be linked to the remainder of the compound).

In one embodiment of the invention, the compound is a polycondensate, ie a polymer whose monomeric units are linked together with the removal of water. The polycondensate can have a linear, branched, hyperbranched or dendritic structure. Preferably the polycondensate has a linear structure or a structure having a low degree of branching.

In addition to all polycondensates having only one type of bond between monomeric units within their molecules, such as urethane bonds, urea bonds, ester bonds, amide bonds or carbonate bonds, the polycondensates of the present invention Also included are polycondensates having at least two different types of bonds, such as urethane bonds and ester bonds, or urethane bonds and urea bonds, or urea bonds and ester bonds at the same time between monomeric units.

Preferred compounds are from polyurethanes, polyureas, polyesters, polyamides, and polycarbonates, more preferably polyurethanes, polycarbonates, polyesters, polyesterpolyurethanes, polyesterpolycarbonates, polyetherpolyurethanes, and poly Ether polycarbonates. The foregoing terms are well known and have meanings well known to those skilled in the art.

According to the invention, the above-mentioned preferred compounds may each further comprise different kinds of bonds between the respective units. Thus, in addition to the urethane bonds resulting from the reaction between R-NCO and R'-OH, polyurethanes may also include urea bonds resulting from the reaction between R-NCO and R'-NH.

Preferred compounds of the invention are polyurethanes. Preferred polyurethanes are selected from polyetherethanes and polyesterurethanes.

Polyol

The polyol contains two or more OH groups. In a preferred embodiment of the invention, the polyurethanes of the invention are in copolymerized form with one or more polyols, polyols having a number average molecular weight M _n in the range from 400 to 12,000 g / mol, more preferably in the range from 400 to 10,000 g / mol. It includes.

Preferred polyols are polyester polyols and polyether polyols.

Polyesterpolyurethanes include polyester polyols (also referred to as “polyesterols”) in the form of co-condensed hydrophilic moieties. Polyester polyols comprise at least two OH groups and at least two ester groups per molecule; The number average molecular weight M _n of such compounds is preferably at least 400 g / mol. Preferred polyester polyols according to the invention have a number average molecular weight M _n in the range from 400 to 5000 g / mol, more preferably from 400 to 2000 g / mol.

Polyester polyols are generally prepared through the reaction of dicarboxylic acids with polyols at high temperatures. Information on the industrial production of polyester polyols is described, for example, in Kunststoffhandbuch Polyurethane, edited by G. Oertel, 3rd edn. 1993, Carl Hanser, section 3.1.2, especially section 3.1.2.3.

Polyetherpolyurethanes include polyether polyols in cocondensed form as hydrophilic moieties. Polyether polyols (also referred to as "polyetherols") comprise at least two OH groups and at least two ether groups per molecule, the M _n of said polyetherols being preferably at least 1000 g / mol.

The hydrophilicity of polyether polyols is generally those which are water soluble at room temperature (20 ° C.). The preparation of polyether alcohols is described in M. Ionescu, "Chemistry and technology of polyols for polyurethanes", Rapra Technology, 2005.

Alkylene oxide starting products frequently used for the production of polyetherols are propylene oxide (PO) and / or ethylene oxide (EO).

Starting compounds contemplated for the preparation of polyetherols include, for example:

a) monoethylene glycol, diethylene glycol, triethylene glycol, PEG, monopropylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polytetrahydrofuran, glycerol, trimethylolpropane, trimethylolethane, neopentyl glycol Sugars and sugar derivatives such as sucrose or sorbitol, bisphenol A, bisphenol F, pentaerythritol, modified starch, water, and mixtures thereof;

b) amines such as ethylenediamine, triethanolamine or tolylenediamine.

The alkylene oxides used are preferably mixtures of two or more of propylene oxide, ethylene oxide, butylene oxide, isobutylene oxide, styrene oxide or alkylene oxides mentioned. As the alkylene oxide, preference is given to using propylene oxide, ethylene oxide or a mixture of propylene oxide and ethylene oxide. Especially preferably the alkylene oxide used is ethylene oxide.

The operation can be carried out either by Landon copolymerization using different alkylene oxides or by block copolymerization.

Particularly suitable polyetherols are, for example, by polymerization of ethylene oxide (EO), products of copolymerization or graft polymerization thereof, and also polyethers obtained by condensation of polyhydric alcohols or mixtures thereof, and by ethoxylation of polyfunctional alcohols. Polyethers, amides, polyamides, and amino alcohols obtained. Examples thereof are, for example, polyethylene glycol, adducts of ethylene oxide and trimethylolpropane, or EO-propylene oxide (PO) block copolymers.

Suitable polyols for the production of the polyurethanes of the invention are preferably polyether polyols which comprise at least mostly polyethylene glycol. Examples of suitable polyethylene glycols are those having an average EO unit in the range of 30 to 450 per polymer molecule.

Other suitable polyether polyols are those having more than two hydroxyl groups. This can be obtained, for example, by adding EO and / or PO with polyhydric alcohols such as glycerol, trimethylolpropane, trimethylolethane, sugars and sugar derivatives such as sucrose or sorbitol, pentaerythritol, or amines.

As a result of the free OH groups, such polyether polyols provide a branching point in the compounds of the present invention.

Preference is given to polyols of the formula HO- (CH ₂ -CH ₂ -O) _n -H, wherein n can be a value in the range from 30 to 450.

The polyetherols preferably have an M _n value in the range of 1500 to 12,000 g / mol, more preferably 10,000 g / mol or less.

In one preferred embodiment of the invention, the polyurethanes obtainable according to the process of the invention comprise one or more polyether polyols in copolymerized form, wherein said one or more polyether polyols are from 1500 to 12,000 g / mol More preferably has a number average molecular weight M _n in the range from 4000 to 10,000 g / mol. Very particularly preferred copolymerized polyetherols have a number average molecular weight M _n in the range of 6000 g / mol to 9000 g / mol.

In one embodiment of the present invention, the polyetherol copolymerized with polyurethane has a number average molecular weight M _n in the range of 5800 to 6200 g / mol.

In another embodiment of the invention, the polyetherol copolymerized with polyurethane has a number average molecular weight M _n in the range of 8800 to 9200 g / mol.

The polyurethanes of the present invention also include low molecular weight compounds having two or more hydroxyl groups or two or more amine groups in copolymerized form. Low molecular weight compounds of this kind having two hydroxyl or amine groups, generally referred to as chain extenders, can be functionalized with ionic groups and are known to those skilled in the art. Low molecular weight compounds having more than two hydroxyl or amine groups serve as branching points in the compounds of the invention.

The polyurethanes of the present invention may also comprise relatively high molecular weight compounds having one hydroxyl group or one amine group in copolymerized form. Examples of such compounds include polyetherols having their etherified OH groups in all bar forms. Examples thereof are polyalkylene glycol alkyl ethers of the formula HO- (R ² -O) _n -alkyl.

Polyisocyanate

Suitable polyisocyanates preferably comprise 2 to up to 4 NCO groups on average, with diisocyanates being particularly preferred.

Examples that can be presented as suitable isocyanates include 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H ₁₂ MDI), xylylene diisocyanate (XDI), tetramethyl Xylene diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,4-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2 when preferred as isomers or mixtures of, 4-phenylene diisocyanate, tolylene diisocyanate (TDI) , 4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-S-isocyanato-1-trimethylcyclohexane, 4,4'- Diisocyanatophenylperfluoroethane, tetramethoxybutane 1,4-diisocyanate, butane 1 , 4-diisocyanate, hexane 1,6-diisocyanate (HDI), dicyclohexylmethane diisocyanate, cyclohexane 1,4-diisocyanate, ethylene diisocyanate, and bisisocyanatoethyl phthalate.

In one preferred embodiment, the polyurethanes of the present invention comprise cycloaliphatic or aliphatic diisocyanate radicals, more preferably aliphatic diisocyanate radicals.

Examples of co-condensed aliphatic diisocyanates include: 1,4-butylene diisocyanate, 1,12-dodecamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2-butyl-2-ethylpenta Methylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and, in particular, hexamethylene diisocyanate (hexane 1,6-diisocyanate, HDI).

Examples of co-condensed cycloaliphatic diisocyanates include: isophorone diisocyanate (IPDI), 2-isocyanatopropylcyclohexyl isocyanate, 4-methylcyclohexane, 1,3-diisocyanate (H-TDI ), And 1,3-bis (isocinanatomethyl) cyclohexane. Additionally, H ₁₂ -MDI or diisocyanate (also known as "saturated MDI") such as 4,4'-methylenebis (cyclohexyl isocyanate) (which is also alternatively dicyclohexylmethane 4,4'-diisocyanate) Or 2,4'-methylenebis (cyclohexyl) diisocyanate may be present as a radical in the polyurethanes of the invention.

In connection with the preparation of the compounds of the invention, it is also possible to use mixtures of the above-mentioned diisocyanates to prepare mixtures of different polyurethanes. One preferred embodiment may use isocyanates having two functional groups (two NCO groups per molecule).

Other embodiments may use isocyanates having more than two functional groups (more than two NCO groups per molecule). Polyurethanes having a structure branched in the isocyanate section are then obtained.

In the preparation of the compounds of the present invention, components reactive to hydroxyl groups and amine groups can be used in amounts in which excess groups reactive to hydroxyl groups and amine groups are present. This excess result allows the end groups of formula (I) to be linked to the remainder of the compound via the reaction of polyethers of formula (I) with -OH-reactive and / or -NH-reactive groups.

In one preferred embodiment of the invention, the compounds of the invention are prepared using an amount of isocyanate groups and optionally chain extenders greater than the amount of OH groups in the polyol. If the compounds of the invention are prepared using only terminal groups, for example diols and diisocyanates, diisocyanates are used in excess moles.

In one embodiment of the invention, the ratio of NCO groups to -NCO-reactive groups in the preparation of the compounds of the invention ranges from 1.2: 1 to 2: 1, preferably 1.4: 1 to 1.8: 1. And -NCO-reactive groups in the polyether of formula (I) are excluded for calculation.

Preferred polyetherpolyurethanes include polyether polyols and polyisocyanates in cocondensed form.

The present invention thus provides the above-described polymers of the present invention, said polymers being polyetherpolyurethanes, each in copolymerized form, comprising:

a. At least one polyether polyol and

b. At least one polyisocyanate.

It is preferred that the molar ratio of the NCO groups of the polyisocyanate to the OH groups of the polyether polyols prior to the polymerization is in the range from 1.2: 1 to 2: 1, preferably in the range from 1.4: 1 to 1.8: 1.

In one preferred embodiment of the invention, the polyetherpolyurethanes of the invention comprise in copolymerized form at least one polyetherdiol as polyol and at least one diisocyanate as polyisocyanate.

In another embodiment of the present invention, the polyetherurethanes of the present invention comprise one or more polyisocyanates having at least one polyetherdiol and at least three isocyanate groups (-NCO) as polyols in cocondensed form. Polyetherpolyurethanes of this invention of this kind are branched in at least hydrophobic sections based on at least trifunctional polyisocyanates.

In another embodiment of the invention, the polyetherpolyurethanes of the invention comprise at least one polyether polyol having at least 3 hydroxyl groups as polyols and at least one diisocyanate as polyisocyanates. Polyetherpolyurethanes of the invention of this kind are branched in at least hydrophilic sections based on at least trifunctional polyether polyols.

In another embodiment of the present invention, the polyetherpolyurethanes of the present invention comprise at least one polyether polyol having at least three hydroxyl groups and at least one polyisocyanate having at least three isocyanate groups in cocondensed form. Include.

In one embodiment of the invention, the polyetherpolyurethanes of the invention have a hyperbranched or dendrimeric structure. The preparation of hyperbranched polyurethanes is for example described in WO 97/02304 or DE 199 04 444.

One particularly preferred embodiment of the present invention relates to the polyurethanes of the present invention having a linear or low degree of branching, wherein the polyisocyanate component and polyol component used in the preparation of the polyurethanes of the present invention have the following composition:

The polyisocyanate component comprises at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, more particularly at least 99% by weight of diisocyanate.

The polyol component comprises at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, more particularly at least 99% by weight of diol, said diol being preferably selected from polyetherdiols.

Polyether Dendron

Compounds of the invention also include one or more end groups of formula (I):

[Wherein, the definition is as follows:

R ¹ : independently in each occurrence C ₄ -C ₄₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₃₀ -aryl, C ₇ -C ₄₀ -aralkyl, C ₇ -C ₄₀ -alkylaryl Or-(R ² -O) _n -R ³ ,

R ² , R ⁴ : in each occurrence independently is C ₂ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, or C ₇ -C ₁₀ -aralkylene;

R ³ : H, C ₁ -C ₄₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₃₀ -aryl, C ₇ -C ₄₀ -aralkyl or C ₇ -C ₄₀ -alkylaryl;

n: 1 to 200;

m: 1 to 6;

p: 0 to 200;

: 화합물의 잔부에의 말단기의 연결이고;

: Linkage of the end group to the remainder of the compound;

With the proviso that when p = 0, the end groups are also NR ⁵ rather than O (R ⁵ may be selected from H and C ₁ -C ₃₀ -alkyl).

R ¹ is preferably C ₁₀ -C ₃₂ - is a _{^{(R 2 -O) n -R 3}} - alkyl, C ₁₀ -C _{32 -} alkenyl, or. More preferably R ¹ is C ₁₀ -C _{32 -} alkenyl or-(R ² -O) _n -R ³ to be. Very preferably R ¹ is-(R ² -O) _n -R ³ . In another preferred embodiment, R ¹ is-(R ² -O) _n -R ³ , wherein R ² is C ₂ -C ₅ -alkylene and R ³ is C ₁₂ -C ₃₀ -alkyl or C ₇ -C ₄₀ -aralkyl).

R ² and R ⁴ independently of one another are preferably C ₂ -C ₁₀ -alkylene, substituted or preferably unsubstituted, for example -CH ₂ -CH _2- , -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₃ )-, -CH (C ₂ H ₅ ) -CH _2- , -CH ₂ -CH (C ₂ H ₅ )-,-(CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH ₂ ) ₅ -,-(CH ₂ ) ₆ -,-(CH ₂ ) ₈ -,-(CH ₂ ) _10- , preferably -CH ₂ -CH _2- , -CH (CH ₃ ) —CH ₂ — or —CH ₂ —CH (CH ₃ ) —, more preferably —CH ₂ —CH ₂ —.

The alkylene radicals R ² may be present in mixtures of each or different alkylene radicals. For example, ethylene and propylene radicals can be mixed. The various alkylene radicals may be present in random order or in block form.

R ³ Is preferably H, C ₁ -C ₂₈ -alkyl, C ₇ -C ₄₀ -aralkyl, or C ₇ -C ₄₀ -alkylaryl. More preferably, R ³ is hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, isocyl, henicosil, Docosyl, tricosyl, tetracosyl, pentacosyl and / or hexacosyl, and very preferably C ₁₂ -C ₂₆ -alkyl such as dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, C ₆ -C ₂₈ -alkyl selected from octadecyl, nonadecyl, ecosil, henicosil, docosyl, tricosyl, tetracosyl, pentacosyl and / or hexacosyl.

Branched isomers of such alkyl radicals, such as 2-ethylhexyl, isododecyl, isotetradecyl, isohexadecyl, isooctadecyl, and isoicosyl can be used as radicals of cycloalkanes or alkenes.

In one embodiment, R ³ is C ₈ -C ₂₀ -alkyl, R ² Is ethylene.

In one embodiment, R ² Is ethylene and R ³ is C ₁₃ -alkyl, more particularly iso-C ₁₃ -alkyl.

n is preferably 2 to 100, more preferably 4 to 50, and very preferably 8 to 40.

m is preferably 2 to 5, more preferably 3 to 4.

p is preferably 0 to 50, more preferably 0 to 20.

The end groups of formula (I) are preferably bonded to the remainder of the compound by reaction of the corresponding polyether monoalcohol of formula (Ia):

Wherein R ¹ , R ² , R ⁴ , m, and p are in accordance with the definition of formula (I) having a group reactive to OH group.

Polyether dendrons of the formula (la) and their preparation are generally known, for example from EP 09165576.1. For their preparation, at least one compound of the formula R ¹ -OH is reacted with glycerol, preferably with reactive glycerol derivatives, more particularly epichlorohydrin. For this reaction, it is preferred to select a molar ratio of the compound of formula R ¹ -OH of 2: 1 to the reactive derivative of glycerol, more particularly epichlorohydrin.

The preparation can be carried out, for example, at a temperature in the range from 20 to 200 ° C, preferably from 80 to 130 ° C.

The preparation can be carried out in the presence of a catalyst . Examples of suitable catalysts include inorganic and organic bases. When epichlorohydrin is used as the reactive glycerol derivative, the base serves to neutralize not only the catalyst but also the HCl obtained. Examples of suitable inorganic bases include alkali metal carbonates and in particular alkali metal hydroxides such as NaOH and KOH. Examples of suitable organic bases include tertiary amines, more particularly triethylamine and diazabicyclo [2.2.2] octane (DABCO), and also pyridine and para-N, N-dimethylaminopyridine.

In one embodiment, the preparation can be carried out in a solvent . Examples of suitable solvents include ethers, more particularly 1,4-dioxane, diisopropyl ether, tetrahydrofuran ("THF"), and di-n-butyl ether. Other suitable solvents are n-butyl acetate ("butyl acetate"), DMSO, N, N-dimethylformamide ("DMF"), and N-methylpyrrolidone, and aromatic solvents such as toluene.

In embodiments where water is removed in the manufacturing process, a water-removing agent may be used, examples of which are molecular sieves, sodium sulfate or magnesium sulfate, or the water formed may be removed by azeotropic distillation. In one embodiment of the invention, the reaction is carried out over 15 minutes to 48 hours, preferably 1 to 24 hours, more preferably 3 to 15 hours.

In one embodiment of the invention, the reaction is carried out in a step, in particular in a number corresponding to the desired m. In this kind of reaction, reactive derivatives of glycerol, more particularly epichlorohydrin, are added in an appropriate number of steps. For stepwise reactions, a possible process is, for example, reacting a defined amount of a compound of formula R ¹ -OH with half the number of moles of glycerol, or especially with epichlorohydrin. Thereafter, an amount corresponding to a quarter of the number of moles of the compound of the formula R ¹ -OH is added and the reaction is carried out with glycerol or a reactive derivative of glycerol. If it is desired to carry out an additional step, then glycerol or a reactive derivative of glycerol is subsequently added in an amount corresponding to one-eighth of the number of moles of the compound of formula R ¹ -OH and the reaction is carried out. In each further step, the number of moles of the compound of formula R ¹ -OH added is correspondingly reduced.

An advantageous feature of the described synthetic route is that there is no need for expensive and inconvenient purification or separation of the reaction mixture after each step.

The central hydroxyl group is a single terminal OH group in the dendrimeric polyether of formula (la) when p = 0.

When p = 0 the terminal groups of formula (I) may have the following aspects:

In one embodiment of the invention, the end groups of formula (I) are contaminated with the product of the incomplete reaction. Incomplete reactions can result in the formation of, for example, the following structural units:

It is a feature of this embodiment that there is a mixture of dendrons with different indices m.

In one embodiment of the invention, the end groups of formula (I) and the above-mentioned partially-reacted end groups are bonded to the remainder of the compound by means of an oxygen atom or via a nitrogen atom.

In a preferred embodiment of the invention, the end groups and partially-reacted end groups of formula (I) are linked by the oxygen atom to the remainder of the compound.

In the present invention, at least one end group of the formula (I) is preferably bonded to the remainder of the compound via a structural unit selected from esters, amides, imides, urethanes, ureas, amines, and ethers.

In the present invention, at least one end group of formula (I) is more preferably bound to the remainder of the compound via a structural unit selected from urethanes and ureas.

The compounds of the present invention may comprise one or more end groups of formula (I) per molecule.

End groups and partially-reacted end groups of formula (I) with P> 0 are corresponding polyether dendrons of formula (Ia), for example p = 0 and / or partially-reacted polyethers, with p = 0 It can be obtained for the alkoxylation of the central OH group of the dendron.

The invention further provides a process for the preparation of a compound of the invention, comprising the following steps:

A) providing a polyol and, if desired, reducing the water content of the polyol;

B) adding a polyisocyanate and, if desired, a catalyst such that the amount of NCO groups in the reaction mixture obtained is greater than the amount of NCO-reactive groups;

C) reacting the reaction mixture obtained in step B);

D) reacting the reaction product from step B) with a polyether of formula (la),

[Wherein, the definition is as follows:

R ¹ : independently in each occurrence C ₄ -C ₄₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₃₀ -aryl, C ₇ -C ₄₀ -aralkyl, C ₇ -C ₄₀ -alkylaryl Or-(R ² -O) _n -R ³ ,

R ² , R ⁴ : in each occurrence independently is C ₂ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, or C ₇ -C ₁₀ -aralkylene;

R ³ : H, C ₁ -C ₄₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₃₀ -aryl, C ₇ -C ₄₀ -aralkyl or C ₇ -C ₄₀ -alkylaryl;

n: 1 to 200;

m: 1 to 6;

p: 0 to 200.

In addition to the materials added in steps A to D, solvents may also be added.

In one embodiment of the invention, the resulting reaction mixture is mixed with water after the reaction has ended, so that an aqueous dispersion is preferably produced. "After the reaction kind" means a time point at which the isocyanate group content based on the reaction mixture with the addition of all reactive substances is less than 5% by weight, preferably less than 1% by weight, more preferably less than 0.1% by weight.

In one embodiment of the invention, the process of the invention uses polyetherol, preferably polyetherdiol, as one or more polyols.

In one embodiment of the invention, the process of the invention uses diisocyanates as one or more polyisocyanates.

In one embodiment of the present invention, the reactants used include compounds having more than two hydroxyl groups per molecule and / or compounds having more than two isocyanate groups per molecule.

The use of such reactants in the preparation of the compounds of the present invention results in further branching in these compounds. The resulting compound thus comprises additional branches in the polymer backbone in addition to the dendron end groups.

Accordingly, the present invention also provides compounds of the invention which comprise additional branches in addition to the branched groups of the formula (I).

menstruum

The process of the invention can be carried out in the presence of a solvent. Solvent, when present, refers to a substance or mixture of substances that is liquid under standard conditions, and under standard conditions, at least one reactive component can be dissolved in an amount of at least 10% by weight based on the solution obtained. Clear to eyes, no phase separation By reactive component is meant any substance which is chemically incorporated into a compound of the invention during the preparation of a compound of the invention. Examples of reactive components in the process of the present invention are polyols, polyisocyanates, compounds having hydroxyl groups, and compounds having isocyanate groups.

In one embodiment of the invention, the portion of the solvent based on the total amount of all materials present in the process of the invention is at least 30% by weight, preferably at least 50% by weight, more particularly at least 70% by weight.

In another embodiment of the invention, the portion of the solvent based on the total amount of all materials present in the process of the invention is 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, more particularly 0.1 wt% or less. One embodiment of the invention is therefore a substantially solvent-free process, also referred to as a melting process.

For the preparation of the compounds of the invention, preference is given to using as many polyols as possible. Removal of water from the polyol can occur in step A by azeotropic distillation, which is dried under reduced pressure, or by other methods known to those skilled in the art. By azeotropic distillation, for example, the water can be removed until the content of water which is reactive to hydroxyl groups, preferably before the addition of polyisocyanate, is approximately 300 ppm.

The preparation for the reaction itself involves, for example, placing the polyol under reduced pressure, completing sufficient removal of water (preferably in the content of water up to approximately 300 ppm) and then miscible the solvent, or with xylene, toluene or acetone The same solvent and polyol can be combined and removed for example by azeotropic distillation to reach a content of water of approximately 300 ppm, in which case however the solvent is not completely removed-instead the polyol in the residual solvent A solution of was used for the reaction in the solution.

The compounds of the present invention can be prepared in one-pot reactions or in multistages, preferably by two-stage processes.

The one-pot reaction for the method involves mixing substantially all of the necessary reactive materials and solvents prior to initiation of the reaction in the reaction chamber (eg round-bottom flasks, cedar flasks, Erlenmeyer flasks, reaction vessels, staged vessels, tubes). And then reacting it (typically with stirring circulation / mixing and heating or cooling). If desired, each component may also not be added during the reaction.

catalyst

Suitable catalysts include in principle all catalysts typically used in polyurethane chemistry. Preference is given to using the catalysts described in WO 2009/135857, pages 14-16. Zinc 2-ethylhexanoate (also referred to as zinc octanoate), zinc n-octanoate, zinc n-decanoate, zinc neodecanoate, zinc ricinoleate, and zinc stearate Catalyst is particularly preferred. More particularly zinc neodecanoate is used.

Cosmetic preparations

The compounds of the present invention are preferably used in cosmetic preparations. The present invention therefore provides cosmetic preparations comprising the compounds of the present invention.

One embodiment of the invention is a moisture-containing cosmetic preparation comprising a compound of the invention.

Formulations of the present invention are aqueous or aqueous-alcohol solutions, O / W (preferably) and W / O emulsions, W / O / W (preferably) and O / W / O emulsions, hydrodisperse formulations, solid-stabilizes It may take the form of formulations, stick formulations, PIT formulations, creams, foams, sprays (pumped sprays or aerosols), gels, gel sprays, lotions, oils, oil gels or mousses and thus are formulated with conventional supplements. Can be.

The formulations of the present invention preferably take the form of gels, foams, mousses, sprays, ointments, creams, emulsions, suspensions, lotions, milks or pastes.

The present invention relates to cosmetic preparations selected preferentially from gels, gel creams, milks, hydro formulations, stick formulations, cosmetic oils and oil gels, mascara, self-tanning preparations, facecare compositions, bodycare compositions, and aftersales preparations. will be. Cosmetic preparations are also understood to include preparations for oral care.

Further cosmetic preparations of the invention are skin cosmetic preparations, especially for skin care. Such preparations are more particularly W / O or, preferably, O / W skin creams, day creams and night creams, eye creams, face creams, anti wrinkle creams, mimic creams, moisturizing creams, whitening creams, vitamin creams, skin lotions, Take the form of a care lotion, and a moisturizing lotion.

Further preferred formulations of the present invention are face masks, cosmetic lotions and cosmetic cosmetics such as concealer sticks, stage make-ups, mascara and eyeshadows, lipsticks, nose pencils, eyeliners, make-up, foundations, blushes, powders, and eye Formulations for use in brow pencils.

Additional formulations of the present invention are anti-acne compositions, insect repellents, shaving compositions, depilatory compositions, integrated care compositions, foot care compositions, and baby care products.

Further preferred formulations of the invention are cleaning, showering, and bathing products. Cleaning, showering and bathing products for the purposes of the present invention include liquid-to-gel-like soaps, clear soaps, fine soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps, and synthetic soaps, pasty soaps, soft soaps. Soaps and cleaning pastes, liquid cleaning, showering, and bathing products such as cleaning lotions, shower lotions and shower gels, foam baths, oil baths, shower oils, and scrub products, and shaving foams, shaving lotions, and shaving creams.

Cosmetic preparations comprising certain polyurethanes are described, for example, in WO # 2009/135857. The compounds of the invention are also generally suitable for use in the preparations described in WO # 2009/135857. The disclosure of WO # 2009/135857 is incorporated herein by reference. In the context of the present invention, the polyurethanes used in the preparation of WO # 2009/135857 are replaced by the compounds of the present invention. The compounds of the invention are thus used in place of the polyurethanes which are preferably used in the preparation of WO # 2009/135857.

Suitable ingredients for the formulations of the invention are described in WO # 2009/135857, page 24 to page 35, hereby incorporated by reference in its entirety.

Also in accordance with the present invention are UV light-blocking cosmetic compositions comprising the compounds of the invention. Light blocking cosmetic compositions are understood in the context of the present invention to be cosmetic preparations comprising at least one UV filter material.

UV light blocking compositions corresponding to the light blocking formulations of the present invention are described in WO # 2009/135857, page 35 to page 42, hereby incorporated by reference in its entirety.

The invention also provides for use in the skin, in the mucosa, in the mucosa, and more particularly in the use of keratin materials such as hair, eyelashes, and eyebrows, especially for their shaping, embellishment, pigmentation, and cosmetics, and also for skin And cosmetic preparations, preferably in liquid or paste-like form, for the management of epidermal derivatives. The formulations of the present invention, which in principle are provided with suitable formulations and colorings, can also be used for make-up, concealer, camouflage, eyeshadow, eyeliner, lip liner, blusher, lip blush, lip gloss, sunscreen composition, sunblock, disposable tattoos, surfers It can be used as a coloring effect sunscreen or the like.

One preferred embodiment of the invention is therefore a cosmetic cosmetic preparation comprising a compound of the invention.

Formulations according to the decorative cosmetic preparations of the present invention are described in WO # 2009/135857, page 43 to page 46, hereby incorporated by reference in its entirety.

The present invention provides an aqueous preparation further comprising one or more salts or surfactants or both in addition to the compounds according to the invention.

Further embodiments of the invention are shampoos and cosmetic cleansing compositions comprising the compounds of the invention.

Formulations corresponding to the shampoo and cosmetic cleansing compositions of the present invention are similarly described in WO # 2009/135857, page 46 to page 55, hereby incorporated by reference in its entirety.

A further embodiment of the invention is a deodorant lotion and deodorant based on an oil-in-water dispersion or an oil-in-water emulsion for the application of deodorants or antiperspirants, more particularly active compounds, more particularly water-soluble active compounds, to the skin comprising the compounds of the invention. Antiperspirant sticks. Agents corresponding to the deodorant and antiperspirant of the present invention are similarly described in WO # 2009/135857, page 55 to page 59, hereby incorporated by reference in its entirety.

A further embodiment of the invention is hair dyes comprising the compounds of the invention.

Formulations corresponding to hair dyes comprising the compounds of the invention are similarly described in WO # 2009/135857, page 59 to page 65, incorporated herein by reference in its entirety.

A further embodiment of the invention is a haircare composition, more particularly a hair conditioner, comprising the compound of the invention.

Haircare compositions corresponding to haircare compositions comprising the compounds of the invention are described in WO # 2009/135857, page 59 to page 67, hereby incorporated by reference in its entirety.

A further embodiment of the invention is an acidic formulation comprising a compound of the invention.

Many cosmetic preparations include active ingredients that express their desirable effect, particularly at acidic pH values. Such formulations include, for example, formulations comprising alpha-hydroxycarboxylic acids (AHA) and beta-hydroxycarboxylic acids (BHA), these components having little or no activity in the neutralized state. . Acidic formulations corresponding to acidic formulations comprising a compound of the present invention are similarly described in WO # 2009/135857, page 67 to page 69, hereby incorporated by reference in its entirety.

A further embodiment of the invention is a self-tanning product comprising a compound of the invention.

Commercial self-tanning products generally constitute O / W emulsions. In such emulsions, the aqueous phase is stabilized by conventional emulsifiers in the cosmetic field.

Uniform skin pigmentation can be achieved through the application of the self-tanning products of the present invention; It is also possible to provide uniform pigmentation for differently colored skin sections as a result of the original or diseased transformation.

Self-tanning materials advantageously used according to the invention include glycerylaldehyde, hydroxymethylglyoxal, γ-dialdehyde, ethyl cellulose, 5-hydroxy-1,4-naphthoquinone (juglon), And also 2-hydroxy-I, 4-naphthoquinone present in henna leaves. Particular preference is given to 1,3-dihydroxyacetone (DHA), a trivalent sugar produced in the human body. 6-Aldo-D-fructose and ninhydrin can also be used as self-tanning agents of the present invention. Self-tanning agents also contemplated in the sense of the present invention are substances that induce skin pigmentation other than brown shades.

In one preferred embodiment of the present invention, such preparations comprise the self-tanning material in a concentration of from 0.1% to 10% by weight, more preferably from 0.5% to 6% by weight, in each case based on the total weight of the preparation. Include.

Such formulations preferably comprise 1,3-dihydroxyacetone as a self-tanning material. Further preferably such compositions comprise organic and / or inorganic light blocking filters. The formulations may also include inorganic and / or organic and / or modified inorganic pigments.

Additional components preferably included in the formulations of the invention are specified, for example, in DE 103 21 147, paragraphs [0024] to [0132] and incorporated herein by reference in their entirety.

The invention further provides for the use of such agents for the coloring of the skin of multicellular organisms, more particularly the skin of humans and animals, in particular for equalizing the color of differently colored sections of the skin.

A further embodiment of the invention is a cleansing comprising an agent for oral and dental care and a compound of the invention.

Oral and dental care and cleansing preparations corresponding to formulations comprising a compound of the invention are described analogously in WO # 2009/135857, page 69 to page 70, hereby incorporated by reference in its entirety.

A further embodiment of the invention is a formulation for hair removal comprising the compound of the invention.

Hair removal formulations corresponding to formulations comprising a compound of the present invention are similarly described in WO # 2009/135857, page 70 to page 71, hereby incorporated by reference in its entirety.

A further embodiment of the invention is a formulation for permanent hair shaping comprising a compound of the invention.

Permanent hair shaping formulations corresponding to formulations comprising a compound of the present invention are similarly described in WO # 2009/135857, page 71 to page 73, hereby incorporated by reference in its entirety.

The present invention provides the use of the polymer of the invention [B1] to increase its compatibility with polar solvents such as ethanol, propylene glycol or glycerol.

The invention likewise provides for the use of the polymers of the invention to increase the solubility of somewhat water soluble components such as hydrophilic UV screens.

The present invention further provides for the use of the polymers of the invention to increase water retention in formulations after application to the skin (moisturizers).

The invention likewise provides for the use of the polymers of the invention for improving the dispersibility of the particles in the formulation.

Experimental part

The invention is described in more detail below by examples, but is not limited to these examples.

Compound A.1 is prepared in 1,4-dioxane dried by standard methods. The molecular weight of A.1 was determined by gel permeation chromatography (GPC) in DMAC (N, N-dimethylacetamide) as a solvent using PMMA as standard.

The molecular weight of A.2 / A.3 was determined by GPC in THF (tetrahydrofuran) as solvent using PMMA as standard.

All reactions were carried out in an atmosphere of inert gas (dried nitrogen).

The amount of% is% by weight unless explicitly stated otherwise.

Determination of dynamic viscosity

The kinematic viscosity of the compounds of the invention in aqueous dispersions was measured at 23 ° C. in the form of a 10 wt% dispersion. The kinematic viscosity was determined at shear rates of 100 l / s and 350 l / s. These two values make it possible to conclude whether the compounds of the present invention exhibit structural viscosity (similar plasticity) or Newton thickener behavior in aqueous dispersions.

The kinematic viscosity was determined according to DIN 53019 using:

Physica Rheolab MCI Handheld Rotational Viscometer (Anton Paar);

-Cylinder measuring system, Z4 DIN cylinder (14 mm diameter)

synthesis Example  One: Polyether Dendron  A. 1 of  Produce

[Wherein,

R ¹ =-(R ² -O) _n -R ³ ;

R ² = -CH ₂ -CH _2- ;

R ³ = approximately 1: 1 part by weight mixture of n-octadecyl (stearyl) and n-hexadecyl (cetyl);

n = 25;

m = 2].

AT25, BASF SE) 의 대략 1:1 중량부 혼합물 200 g (147　mmol) 의 용액으로 충전하였다. 교반하면서 24 g 의 KOH 펠렛 (428　mmol) 을 첨가하였다. 혼합물을 100 ℃ 로 가열하고, 이후 25 ml 의 디옥산 중의 용액에서 6.8 g (73.5 mmol) 의 에피클로로히드린을 30 분의 기간에 걸쳐 적가하였다. 혼합물을 2 시간 동안 교반하고, 이후 25 ml 의 디옥산 중의 용액에서의 추가 3.4　g (36.8　mmol) 의 에피클로로히드린을 30 분의 기간에 걸쳐 적가하였다. 이에 이어 2 시간 초과 동안 교반하고, 이후 다시 25 ml 의 디옥산 중의 용액에서의 1.7　g (18.4　mmol) 의 에피클로로히드린을 15 분의 기간에 걸쳐 적가하였다. 혼합물을 105 ℃ 에서 추가 15 시간의 기간 동안 교반한 후, 실온 (25 ℃) 로 냉각시켰다. 형성된 침전물을 여과하고, 디옥산을 30 mbar 에서 증류시켰다. 점성의 연한 갈색 오일로서의 화합물 A.1 을 얻었고, 이를 MS (MALDI TOF) 및 GPC 로 특정하였다. M_n: 4400 g/mol, M_w: 6600 g/mol.Dropping funnel, magnetic stirrer, and a reflux condenser, a 1-liter flask 525 ml of dioxane in the polyethylene glycol mono-cetyl ether _{having, CH 3 - (CH 2)} 15 -O- (CH 2 - CH 2 -O) ₂₅ H and polyethylene glycol stearyl _{ether, CH 3 - (CH 2)} 17 -O- (CH 2 - CH 2 -O) 25 H (Lutensol

AT25, BASF SE) was charged with a solution of 200 g (147 mmol) of a approximately 1: 1 weight mixture. 24 g KOH pellets (428 mmol) were added with stirring. The mixture was heated to 100 ° C. and then 6.8 g (73.5 mmol) of epichlorohydrin in a solution in 25 ml of dioxane was added dropwise over a period of 30 minutes. The mixture was stirred for 2 hours, after which additional 3.4 g (36.8 mmol) of epichlorohydrin in a solution in 25 ml of dioxane were added dropwise over a period of 30 minutes. This was followed by stirring for more than 2 hours, after which again 1.7 g (18.4 mmol) of epichlorohydrin in a solution in 25 ml of dioxane were added dropwise over a period of 15 minutes. The mixture was stirred at 105 ° C. for a further 15 h period and then cooled to room temperature (25 ° C.). The precipitate formed was filtered off and the dioxane was distilled at 30 mbar. Compound A.1 was obtained as a viscous light brown oil which was characterized by MS (MALDI TOF) and GPC. M _n : 4400 g / mol, M _w : 6600 g / mol.

synthesis Example  2: Polyether Polyurethane  A. 2 of  Produce

E6000 (BASF SE, 분자량 6000 g/mol) 을 질소 하에 2 l 중합 반응기에서의 334.00 g 의 자일렌에 용해시켰다. 용액을 대략 140 ℃ (내부 온도) 로 가열한 후, 200　g 의 자일렌을 증류시켰다. 반응 혼합물의 수분 함량은 이후 대략 70 ppm 이었다. 중합체 용액을 이후 50 ℃ (내부 온도) 로 냉각시키고 2.5 ml 의 자일렌 중의 용액에서 53　mg 의 아세트산과 혼화하여, 폴리에틸렌 글리콜에서 앞서 정량적으로 결정한 양의 아세트산칼륨을 중화시켰다. 2.5 ml 의 자일렌 중의 용액에서의 180　mg 의 아연 네오데카노에이트 (TIB Kat 616) 및 5 ml 의 자일렌 중의 용액에서의 2.94 g 의 헥사메틸렌 디이소시아네이트의 첨가에 의해, 중합이 개시되었고, 0.25 중량% 의 이소시아네이트 함량에 도달할 때까지 반응 혼합물을 50 ℃ 의 내부 온도에서 반응시켰다. 이후 66　ml 의 자일렌 중의 용액에서의 66.0 g 의 화합물 A.1 을 첨가하고 반응 혼합물을 0 % 의 이소시아네이트 함량에 도달할 때까지 반응 혼합물을 50 ℃ 의 내부 온도에서 반응시켰다. 자일렌 용매를 증가된 온도 (60 ℃) 에서 진공 증류에 의해 대부분 제거하였고 (잔류 함량 < 100 ppm), 잔류물을 515.8 g 의 물에 용해시켰다. 수용액을 실온 (25 ℃) 으로 냉각시킨 후, 이를 마지막으로 6.45 g 의 보존제 Euxyl

K701 및 70　mg 의 안정화제 4-히드록시-TEMPO 와 혼화시켰다. 이로서 18.7 중량% 의 고형분을 갖는 수분산액의 형태로 중합체 A.2 (M_n = 8700 g/mol; M_w = 31　100 g/mol) 를 얻었다.60.00 g of polyethylene glycol Pluriol

E6000 (BASF SE, molecular weight 6000 g / mol) was dissolved in 334.00 g of xylene in a 2 l polymerization reactor under nitrogen. After heating the solution to approximately 140 ° C. (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then approximately 70 ppm. The polymer solution was then cooled to 50 ° C. (internal temperature) and mixed with 53 mg of acetic acid in a solution in 2.5 ml of xylene to neutralize the previously determined quantity of potassium acetate in polyethylene glycol. The polymerization was initiated by the addition of 180 mg of zinc neodecanoate (TIB Kat 616) in solution in 2.5 ml xylene and 2.94 g of hexamethylene diisocyanate in solution in 5 ml xylene, 0.25 The reaction mixture was reacted at an internal temperature of 50 ° C. until an isocyanate content of weight percent was reached. 66.0 g of compound A.1 in a solution in 66 ml xylene were then added and the reaction mixture was reacted at an internal temperature of 50 ° C. until the reaction mixture reached 0% isocyanate content. The xylene solvent was mostly removed by vacuum distillation at increased temperature (60 ° C.) (residual content <100 ppm) and the residue was dissolved in 515.8 g of water. After cooling the aqueous solution to room temperature (25 ° C.), it was finally added to 6.45 g of preservative Euxyl

K701 and 70 mg of stabilizer 4-hydroxy-TEMPO. This resulted in polymer A.2 (M _n = 8700 g / mol; M _w = 31 100 g / mol) in the form of an aqueous dispersion having 18.7% by weight solids.

The viscosity of the 10 wt% steel aqueous solution of polyetherpolyurethane A.2 was 20 mW 500 mPa * s (shear rate 100 l / s) or 10 m000 mPa * s (shear rate 350 l / s).

synthesis Example  3: Polyether Polyurethane  Preparation of A.3 (Comparison)

E6000 를 질소 하에 2 l 중합 반응기에서의 467.00 g 의 자일렌에 용해시켰다. 용액을 대략 140 ℃ (내부 온도) 로 가열한 후, 200　g 의 자일렌을 증류시켰다. 반응 혼합물의 수분 함량은 이후 대략 100 ppm 이었다. 중합체 용액은 이후 50 ℃ (내부 온도) 로 냉각시키고, 5　ml 의 자일렌 중의 용액에서의 107　mg 의 아세트산과 혼화하여, 폴리에틸렌 글리콜에서 앞서 정량적으로 결정한 양의 아세트산칼륨을 중화시켰다. 5 ml 의 자일렌 중의 용액에서의 360　mg 의 아연 네오데카노에이트 (TIB Kat 616) 및 10 ml 의 자일렌 중의 용액에서의 5.88 g 의 헥사메틸렌 디이소시아네이트의 첨가에 의해, 중합이 개시되었고, 대략 0.26 % 의 이소시아네이트 함량에 도달할 때까지 반응 혼합물을 50 ℃ 의 내부 온도에서 반응시켰다. 이후 40.8　ml 의 자일렌 중의 용액에서의 폴리에틸렌 글리콜 모노세틸 에테르, CH₃-(CH₂)₁₅-O-(CH_{2 --}CH₂-O)₂₅H, 및 폴리에틸렌 글리콜 모노스테아릴 에테르, CH₃-(CH₂)₁₇-O-(CH_{2 --}CH₂-O)₂₅H (Lutensol

AT25, BASF SE) 의 대략 1:1 중량부 혼합물 40.8 g 을 첨가하고, 이소시아네이트 함량이 0 % 에 도달할 때까지 반응 혼합물을 50 ℃ 에서 가열하였다. 자일렌 용매를 이후 증가된 온도 (60 ℃) 에서 진공 증류에 의해 대부분 제거하고 (잔류 함량 < 100 ppm), 잔류물을 666.7 g 의 물에 용해시켰다. 수용액을 실온 (25 ℃) 으로 냉각시킨 후, 이를 마지막으로 8.34 g 의 보존제 Euxyl

K701 및 80　mg 의 안정화제 4-히드록시-TEMPO 와 혼화시켰다. 이로서 22.6 중량% 의 고형분을 갖는 수분산액의 형태로 중합체 A.3 (M_n = 10,100 g/mol; M_w = 35,000 g/mol) 를 얻었다.120.00 g of polyethylene glycol Pluriol

E6000 was dissolved in 467.00 g of xylene in a 2 l polymerization reactor under nitrogen. After heating the solution to approximately 140 ° C. (internal temperature), 200 g of xylene were distilled off. The water content of the reaction mixture was then approximately 100 ppm. The polymer solution was then cooled to 50 ° C. (internal temperature) and mixed with 107 mg of acetic acid in a solution in 5 ml of xylene to neutralize the amount of potassium acetate previously determined quantitatively in polyethylene glycol. The polymerization was initiated by the addition of 360 mg of zinc neodecanoate (TIB Kat 616) in solution in 5 ml xylene and 5.88 g of hexamethylene diisocyanate in solution in 10 ml xylene, approximately The reaction mixture was reacted at an internal temperature of 50 ° C. until reaching an isocyanate content of 0.26%. After 40.8 ml of a xylene solution of the polyethylene glycol cetyl ether _{in, CH 3 - (CH 2)} 15 -O- (CH 2 - CH 2 -O) 25 H, and polyethylene glycol stearyl ether, CH ₃ -(CH ₂ ) ₁₇ -O- (CH _{2 -} CH ₂ -O) ₂₅ H (Lutensol

AT25, BASF SE) was added 40.8 g of approximately 1: 1 parts by weight mixture, and the reaction mixture was heated at 50 ° C. until the isocyanate content reached 0%. The xylene solvent was then mostly removed by vacuum distillation at increased temperature (60 ° C.) (residual content <100 ppm) and the residue was dissolved in 666.7 g of water. After cooling the aqueous solution to room temperature (25 ° C.), it was finally 8.34 g of preservative Euxyl

K701 and 80 mg of stabilizer 4-hydroxy-TEMPO. This gave polymer A.3 (M _n = 10,100 g / mol; M _w = 35,000 g / mol) in the form of an aqueous dispersion having a solid content of 22.6% by weight.

The viscosity of the 10 wt% steel aqueous solution of polyetherpolyurethane A.3 was 1750 mPa * s (shear rate 100 l / s) or 1550 mPa * s (shear rate 350 l / s).

Cosmetic formulations FA.2 and FA.3 were prepared by adding oil phase A to water phase B and then admixing the obtained O / W emulsion with a preservative (phase C).

Typical preparations of the invention are described below, but this invention is not limited to these examples.

Percentages are by weight unless explicitly stated otherwise.

Produce

Phases A and B are separately heated to approximately 80 ° C.

Stir phase B into phase A and homogenize briefly.

Cool to approximately 40 ° C. with stirring, add phase C, cool to room temperature with stirring, and homogenize again briefly.

Produce

Phase A is heated to 80 ° C. Add phase B to phase A.

Phase A + B is homogenized for 3 minutes.

Phase C is heated to 80 ° C., stirred into phase A + B and homogenized.

The emulsion is cooled to 40 ° C. with stirring.

Phase D is added, cooled to room temperature with stirring and homogenized.

Produce

Phases A and B are separately heated to approximately 80 ° C.

Stir phase B into phase A and homogenize briefly.

Cool to approximately 40 ° C. with stirring, add phase C, cool to room temperature with stirring, and homogenize again briefly.

Produce

Phases A, B, C and D are heated to 70 ° C. separately from each other.

Homogenize phase B in a triple-roll mill. Stir phase B into phase A.

Again homogenize the whole briefly.

Dissolve phase C, add to phase A + B and stir.

Phase D is dissolved and placed in combined phase A + B + C and homogenized.

Cool to approximately 40 ° C. with stirring, add phase E and cool to room temperature.

Homogenize briefly.

Produce

Phase A is heated to 80 ° C.

Phase B is heated to approximately 80 ° C. and injected into phase A with stirring. Homogenize.

Cool to approximately 40 ° C. with stirring, add phase C + D and cool to room temperature with stirring.

Homogenize briefly.

Produce

Phases A and B are heated to approximately 80 ° C. separately from each other.

Stir phase B into phase A with homogenization followed by short homogenization.

Cool to approximately 40 ° C., add phases C and D with homogenization, and allow to cool to room temperature with stirring.

Produce:

I: Weigh phases A and B separately and inject and heat to 80 ° C. with stirring.

II: Combine phases A and B at 80 ° C. with stirring.

III: Cool to room temperature with stirring.

Produce:

I: Weigh phases A, B and C separately and inject, if necessary, stir until homogenized at room temperature.

II: Combine phases B and A with stirring at room temperature and stir until homogenous, then add phase C with stirring and stir well.

Produce:

1. Weigh and inject compound of phase A with stirring until complete dissolution in the order listed.

2. Weigh and inject the compound of phase B while stirring and heating at 40-45 ° C.

3. Combine phases A and B and transfer to a suitable propellant gas container for the hair mousse.

4. Seal and fill with propellant gas phase C.

Produce

Phases A and B are separately heated to approximately 80 ° C.

Stir and homogenize phase B into phase A.

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

Cool to approximately 40 ° C. with stirring.

Put in phase C, stir and short homogenize.

Cool to room temperature with stirring.

Phases A and B are heated to approximately 80 ° C. Stir phase B into phase A and homogenize. Stir until cooled, place in phase C, stir again and homogenize briefly.

Examples of hydroxy acids that can be used are as follows:

Alpha-hydroxy acids: lactic acid, citric acid, malic acid, glycolic acid

Dihydroxy acid: tartaric acid

Beta-hydroxy acid: salicylic acid

Produce

Phases A and B are separately heated to approximately 80 ° C. Optionally, the pH of phase B is adjusted to 3 with NaOH.

Stir phase B into phase A with homogenization and short homogenize again.

Cool to approximately 40 ° C., add phase C and homogenize again.

Produce

Phase A and Phase B are separately heated to approximately 75 ° C. Stir and homogenize phase B into phase A. Stir until cooled. Add phase C at approximately 30 ° C.

Note: The formulation is prepared without inert gas. The filling must be made in an oxygen-impermeable pack, for example an aluminum tube.

Produce

Phases A and B are separately heated to approximately 80 ° C.

Stir phase B into phase A with homogenization and short homogenize again.

Cool to about 40 ° C., add phase C and homogenize again.

Produce

Phases A and B are separately heated to approximately 80 ° C.

Stir phase B into phase A with homogenization and short homogenize again.

Cool to approximately 40 ° C., add phase C and homogenize again.

Produce

Weigh phase A and dissolve: Adjust pH to 6-7. Phase B is added and heated to 50 ° C. Allow to cool to room temperature while stirring.

The compounds of the present invention are also useful in the manufacture of hair styling, more particularly hair mousse (aerosol mousse with propellant gas, and pump-type mousse without propellant gas), hair spray (pump-free spray without propellant gas), and hair gels. Can be used.

Propellants are commonly used propellants. Preference is given to mixtures of propane / butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152 a), carbon dioxide, nitrogen or compressed air.

Suitable formulations according to the invention for styling sprays may have the following exemplary compositions.

Produce

Phases A and B are heated separately at approximately 80 ° C.

Stir and homogenize phase B into phase A.

Mix the components of phase C and stir until dissolved.

Add phase C at 30 ° C. and stir until homogenized.

Add phase D and homogenize.

Produce

Phases A and B are heated separately at approximately 80 ° C.

Stir phase B into phase A and homogenize briefly.

Cool to approximately 40 ° C. with stirring, add phase C, and homogenize again briefly.

Claims (10)

Compounds comprising at least one group of formula (I):

[Wherein, the definition is as follows:
R ¹ : independently in each occurrence C ₄ -C ₄₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₃₀ -aryl, C ₇ -C ₄₀ -aralkyl, C ₇ -C ₄₀ -alkylaryl Or-(R ² -O) _n -R ³ ,
R ² , R ⁴ : in each occurrence independently is C ₂ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene, or C ₇ -C ₁₀ -aralkylene;
R ³ : H, C ₁ -C ₄₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₃₀ -aryl, C ₇ -C ₄₀ -aralkyl or C ₇ -C ₄₀ -alkylaryl;
n: 1 to 200;
m: 1 to 6;
p: 0 to 200;

: Linkage of the end group to the remainder of the compound;
With the proviso that when p = 0, the end groups are also NR ⁵ rather than O (R ⁵ may be selected from H and C ₁ -C ₃₀ -alkyl). The compound of claim 1, wherein R ¹ is — (R ² —O) _n —R ³ R ² is C ₂ -C ₅ -alkylene, R ⁴ is C ₂ -C ₅ -alkylene, R ³ is C ₁₂ -C ₃₀ -alkyl or C ₇ -C ₃₀ -aralkyl, p Compound with = 0. A compound according to claim 1 or 2, wherein m is 2-5. The compound according to claim 1, which is selected from urethanes, ureas, esters, amides, and carbonates. The compound of claim 4 which is a polyetherurethane and each comprises the following in copolymerized form:
a. At least one polyether polyol and
b. At least one polyisocyanate. 6. The method of claim 5, wherein said at least one polyether polyol a. A compound having a number average molecular weight M _n in the range of 4000 to 10,000 g / mol. 7. The remainder of the compound according to any one of claims 1 to 6, wherein at least one end group of formula (I) is bonded to the remainder of the compound via a structural unit selected from esters, amides, imides, urethanes, ureas, amines, and ethers. Compound. 8. The compound according to claim 1, wherein at least one end group of formula (I) is bonded to the remainder of the compound via a structural unit selected from urethanes and ureas. 9. An aqueous formulation comprising at least one compound according to claim 1. The aqueous formulation of claim 9 comprising at least one salt or surfactant or both.