CN104042453A

CN104042453A - Cosmetic composition

Info

Publication number: CN104042453A
Application number: CN201310095657.6A
Authority: CN
Inventors: 熊晓辉; 朱中卫
Original assignee: Bayer MaterialScience China Co Ltd
Current assignee: Covestro Deutschland AG
Priority date: 2013-03-13
Filing date: 2013-03-13
Publication date: 2014-09-17
Anticipated expiration: 2033-03-13
Also published as: CN104042453B

Abstract

The invention relates to a cosmetic composition, and especially relates to a hair fixing composition, its application in hair fixing, and its use method. The composition includes special polyurethane and an amphoteric copolymer. Compared with cosmetic compositions in the prior art, the cosmetic composition provided by the invention has the advantages of curling maintenance under high humidity, high elasticity, easy washing and comfortable hair feeling.

Description

Cosmetic composition

Technical Field

The present invention relates to a cosmetic composition comprising a polyurethane and its use in hair styling.

Background

Both human and animal hair belong to keratin fibres. The composition for setting the hair is one of cosmetic compositions, and can be used for setting and stabilizing various hair styles. Hair styling compositions are primarily presented in the form of styling mousses or sprays. Styling mousses and sprays differ little in their composition, but in their application. Styling mousses are applied to damp hair as an aid to model the style. In contrast, hair spray is sprayed onto dry, already styled hair to fix the hairstyle. In addition to hair spray and styling mousse, there are also forms of hair styling gels.

For hair sprays and styling mousses, the composition used for setting or shaping the hair style is generally in the form of a formulation which can be sprayed from an aerosol container, squeezed from a bottle, and also applied by a foaming device. It consists of alcoholic or hydro-alcoholic solution of film-forming natural or synthetic polymers. These polymers can be chosen from nonionic, cationic, amphoteric or anionic polymers. For hair styling gels, the formulations described above are adjusted to acceptable viscosities by using conventional thickeners.

The film-forming polymers used in the prior art are preferably anionic or amphoteric polymers based on acrylates. Typical acrylate film-forming polymers exhibit low moisture and/or water resistance when the hair is contacted with rain or sweat, and/or under the influence of high atmospheric humidity.

The use of polyurethanes in hair styling compositions is known. EP1049446A describes the use of certain polyurethanes in aerosol compositions for hair care. EP1049443A describes the use of certain polyurethanes in aerosols for hair care, wherein the formulation consists of 0.1 to 20% of polycondensates of polyurethanes and/or polyureas, 7.5 to 70% of organic solvents, 15 to 85% of propellants and 0.01 to 20% of at least one polyol.

Compositions for hair styling are also described in the following patents: EP0751162, EP0637600, FR2743297, WO94/03510 and EP 0619111. EP0637600, WO94/03510 and EP0619111 describe polyurethanes containing at least one diol having acid or salt groups, in particular dimethylolpropionic acid or N-methyldiethanolamine. EP0751162 and FR2743297 describe chain-segmented polyurethane and/or polyurea polycondensates consisting of at least one polysiloxane block (FR2743297) or of at least one polyurethane and/or polyurea block containing polysiloxane graft branches (EP0751162), wherein the polyurethane block consists of at least one diol containing acid or salt groups, in particular dimethylolpropionic acid.

EP1457196A describes hair care compositions for aerosols, consisting of water, at least one organic solvent, at least one polyurethane and at least one dimethyl ether (DME) propellant and at least one C3-4 hydrocarbon. Preferred polyurethanes are composed of divalent C2-C10 groups (preferably dimethylolpropionic acid) containing carboxylic or sulfonic acid groups. Luviset PUR (INCI name: polyurethane-1) and Luviset SiPUR A (INCI name: polyurethane-6 ═ dimethylolpropionic acid, isophorone diisocyanate, neopentyl glycol, copolymers of polyester diols and silicone diamines) are used to improve the sensory properties of hair styling sprays.

DE19541326A describes water-soluble or water-dispersible polyurethanes of the following components:

a) water-soluble or water-dispersible urethane prepolymers having terminal isocyanate groups and

b) at least one primary or secondary amine having at least one ionogenic gene or group, and salts thereof.

The urethane prepolymer has high hydrophilicity. The polyurethane is therefore more washable than other polyurethane polymers of the prior art.

However, the above-listed patents do not mention important properties of film-forming agents, such as water vapor resistance or water resistance and curl retention at high temperatures.

US12/934849 discloses hair styling compositions comprising at least one polyurethane obtained by reacting one or more water-insoluble, non-water-dispersible isocyanate-functional polyurethane prepolymers with one or more amino-functional compounds. The composition has good water resistance and curl retention at high temperatures. However, the above patent publication does not mention other properties of the hair styling composition, such as the wash-off property and the hair feel property.

US12/707796 discloses hair styling compositions in which a vinyl pyrrolidone homo-or copolymer is added to the hair styling composition disclosed in US12/934849, whereby the resulting composition is capable of forming a soft film on the hair with a high styling ability.

The entire contents of the above patents and patent publications are incorporated herein by reference.

Summary of The Invention

There is a need in the market today for low VOC hair styling compositions. An ideal hair styling composition should have shampoo-washability and a pleasant hair feel, while having high water resistance and curl retention at high humidity.

It is an object of the present invention to provide a cosmetic composition, in particular a hair styling composition, comprising a polyurethane. The composition has high water resistance and curl retention under high humidity, as well as easy shampoo washability, excellent hair film hardness and elasticity, and comfortable hair feel.

In one aspect, the present invention discloses a cosmetic composition comprising an aqueous dispersion of at least one polyurethane a) obtainable by reacting one or more water-insoluble, non-water-dispersible isocyanate-functional polyurethane prepolymers a1) with one or more amino-functional compounds a 2); further comprising at least one amphoteric copolymer B).

Wherein a1) is obtainable by reacting one or more polyols selected from polyether polyols, polycarbonate polyols, polyether polycarbonate polyols and/or polyester polyols with polyisocyanates, for example hexamethylene diisocyanate and/or isophorone diisocyanate.

A2) Comprising an amino-functional compound a2-I having no ionic group or ionogenic group and/or an amino-functional compound a2-II having an ionic group and/or ionogenic group, and a2-I may be a diamine.

The amphoteric copolymer B) comprises at least two monomers B1) and B2), wherein the monomer B1) is selected from any one or any mixture of acrylic acid, methacrylic acid, alkyl acrylate and alkyl methacrylate; monomer B2) is amphoteric and is selected from (meth) acryloylalkyl betaines of formula B2-I:

and/or a (meth) acryloyloxyalkyl amine oxide represented by the formula B2-II:

wherein R is¹Optionally H or CH₃，R²And R³Each independently a straight or branched chain C₁-C₁₀Alkyl, and n represents an integer of 1 to 20.

In another aspect, the present invention also discloses the use of a cosmetic composition as described above for shaping and/or styling keratin fibres and a method for shaping and/or styling keratin fibres.

The cosmetic composition disclosed in the present invention, when applied to keratin fibers (hair), can form a hair film having softness and elasticity, and has a long-lasting setting ability, excellent water vapor resistance and/or water resistance, and curl retention under high humidity. In addition, the shampoo has excellent washing-off property.

Detailed Description

In the context of the present invention, the term "water-insoluble, water-nondispersible polyurethane prepolymer" means that the solubility of the prepolymer in water at 23 ℃ is less than 10 g/l, preferably less than 5 g/l, and that the prepolymer does not give rise to sedimentation-stable dispersions in water (in particular deionized water) at 23 ℃. In other words, in the experiment of dispersing it in water, the prepolymer precipitated out.

Preferably, the polyurethane prepolymer a1) used according to the invention has terminal isocyanate groups, i.e. the isocyanate groups are at the chain ends of the prepolymer. The prepolymer particularly preferably has an isocyanate group at all chain ends.

Furthermore, the polyurethane prepolymers a1) used according to the invention preferably have substantially neither ionic groups nor ionogenic groups, i.e. the content of ionic groups and ionogenic groups is suitably less than 15 milliequivalents (milliequivalents) per 100g of polyurethane prepolymer a1), preferably less than 5 milliequivalents, particularly preferably less than 1 Milliequivalent and very particularly preferably less than 0.1 Milliequivalent per 100g of polyurethane prepolymer a 1).

The amino-functional compounds A2) are preferably selected from primary and/or secondary amines and/or diamines. In particular, the amino-functional compound a2) comprises at least one diamine. Amino-functional compounds A2) are preferably amino-functional compounds A2-II) having ionic groups or ionogenic groups, and amino-functional compounds A2-I) which do not have ionic groups or ionogenic groups.

In a particularly preferred embodiment of the present invention, the amino-functional compound a2) comprises at least one amino-functional compound a2-II) having ionic and/or ionogenic (ion-forming) groups. The ionic groups and/or ionogenic groups used are particularly preferably sulfonate groups or sulfonic acid groups, even more preferably sodium sulfonate groups.

In a further preferred embodiment of the present invention, amino-functional compounds a2) include both amino-functional compounds a2-II) having ionic groups and/or ionogenic groups and amino-functional compounds a2-I) having no ionic groups or ionogenic groups.

The hair styling compositions according to the invention, in particular aqueous (i.e. aqueous) compositions, wherein the polyurethane is present in dispersed form, i.e. substantially in non-dissolved form. Water generally constitutes the major constituent (> 50% by weight) of the dispersion medium, in addition to other liquid media such as solvents that may be present, based on the total amount of liquid dispersion medium in the cosmetic composition.

The cosmetic composition according to the invention preferably has a Volatile Organic Compound (VOC) content of less than 80% by weight, more preferably less than 55% by weight, even more preferably less than 40% by weight, based on the cosmetic composition.

The aqueous polyurethane dispersions used in the preparation of the cosmetic compositions according to the invention preferably have a Volatile Organic Compound (VOC) content of less than 10% by weight, more preferably less than 3% by weight, even more preferably less than 1% by weight, based on the aqueous polyurethane dispersion.

The Volatile Organic Compound (VOC) content is determined in the context of the present invention by gas chromatography analysis.

The water-insoluble and water-nondispersible isocyanate-functional polyurethane prepolymers A1) used according to the invention have essentially neither ionic groups nor ionogenic groups. Water here refers to deionized water without added surfactant. In the context of the present invention, this means that the proportion of ionic and/or ionogenic (ion-forming) groups, such as anionic groups (for example carboxylate or sulfonate) or cationic groups, is less than 15 meq/100 g of polyurethane prepolymer A1), preferably less than 5 meq, particularly preferably less than 1 meq and very particularly preferably less than 0.1 meq/100 g of polyurethane prepolymer A1).

The acid number of the prepolymer in terms of acidic ionic groups and/or ionogenic groups is suitably less than 30mg KOH/g prepolymer, preferably less than 10mg KOH/g prepolymer. The acid number represents the mass (mg) of potassium hydroxide required to neutralize 1g of the investigated sample (measured according to DIN EN ISO 211). The neutralized acid (i.e., the corresponding salt) naturally has no acid value or has a reduced acid value. The acid number of the corresponding free acid is decisive here according to the invention.

Prepolymer a1) used in the preparation of the polyurethanes is preferably obtainable by reacting one or more polyols selected from polyether polyols, polycarbonate polyols, polyether polycarbonate polyols and/or polyester polyols with polyisocyanates, as will also be explained in detail below.

Particularly preferred polyurethanes are obtained by using polymeric polyether polyols and/or polymeric polycarbonate polyols and/or polyether-polycarbonate polyols or polyester polyols, each of these polymers having a number average molecular weight of preferably from about 400 to about 6000g/mol (here and for the following molecular weight data, the molecular weight is determined by gel permeation chromatography in tetrahydrofuran at 23 ℃ C. against polystyrene standards). Their use in the preparation of polyurethanes or polyurethane prepolymers will, as a result of reaction with polyisocyanates, lead to the formation of corresponding polyether and/or polycarbonate and/or polyether-polycarbonate segments or polyester segments in the polyurethanes having the corresponding molecular weights of these segments. According to the invention, particularly preferred are polyurethanes obtained from polymeric polyether diols and/or polymeric polycarbonate diols and/or polyether-polycarbonate polyols or polyester polyols having a linear structure.

The polyurethanes according to the invention are preferably linear molecules, but may also be branched.

The number average molecular weight of the polyurethanes preferably used according to the invention is, for example, about 1000-.

The polyurethanes contained in the cosmetic compositions according to the invention are added to said compositions, in particular in the form of aqueous dispersions.

Preferred polyurethanes or polyurethane dispersions for use according to the present invention can be obtained by methods known in the art using known components, for example U.S. patent publication US2011/0027211, which is hereby incorporated by reference in its entirety. The corresponding steps are briefly described as follows:

a) preparation of an isocyanate-functional polyurethane prepolymer formed from the following Components A1)

An organic polyisocyanate, wherein the polyisocyanate is selected from the group consisting of,

the polymer polyols preferably have a number average molecular weight of 400-8000g/mol (determined here and for the following molecular weight data by gel permeation chromatography in tetrahydrofuran at 23 ℃ relative to polystyrene standards), more preferably 400-6000g/mol and particularly preferably 600-3000g/mol, and an OH functionality of preferably 1.5 to 6, more preferably 1.8 to 3, particularly preferably 1.9 to 2.1,

optionally a hydroxy-functional compound having a molecular weight of preferably 62 to 399g/mol, and

optionally a non-ionic hydrophilizing agent,

and

b) some or all of their free NCO groups are then reacted with one or more amino-functional compounds A2), such as primary and/or secondary amines and/or diamines. The polyurethane used according to the invention is preferably dispersed in water before, during or after step b).

The reaction with the diamine or two or more diamines in step b) is particularly preferably carried out with chain extension. In this regard, monofunctional amines can additionally be added as chain terminators to control molecular weight.

As component A2), it is possible in particular to use amines which have no ionic groups or ionogenic groups, such as anionically hydrophilicizing groups (component A2-I) below), and it is possible to use amines which have ionic groups or ionogenic groups, such as anionically hydrophilicizing groups (component A2-II) below).

The polyurethanes used according to the invention preferably have anionic groups, preferably sulfonate groups. These anionic groups are incorporated into the polyurethane A) via the amine component A2-II) reacted in step b). The polyurethanes of the invention optionally additionally have nonionic components for hydrophilization. Particularly preferred polyurethanes have only sulfonate groups to achieve hydrophilization; these are incorporated into the polyurethane via the corresponding diamines as component A2-II).

In order to achieve good sedimentation stability, the number-average particle size of the polyurethane dispersions of the invention is preferably below 750nm, particularly preferably below 500nm, as determined by laser correlation spectroscopy after dilution with deionized water (instrument: Malvern Zetasizer1000, Malverer Inst.Limited).

Suitable organic polyisocyanates are the aliphatic, aromatic or cycloaliphatic polyisocyanates known to the person skilled in the art having an NCO functionality of greater than or equal to 2.

Non-limiting examples of such polyisocyanates are 1, 4-butylidene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), 2, 2, 4-and/or 2, 4, 4-trimethylhexamethylene diisocyanate, the bis (4, 4 ' -isocyanatocyclohexyl) methane isomer or mixtures of these isomers, 1, 4-cyclohexylidene diisocyanate, 4-isocyanatomethyl-1, 8-octane diisocyanate (nonane triisocyanate), 1, 4-phenylene diisocyanate, 2, 4-and/or 2, 6-toluene diisocyanate, 1, 5-naphthylidene diisocyanate, 2, 2 ' -and/or 2, 4 ' -and/or 4, 4' -diphenylmethane diisocyanate, 1, 3-and/or 1, 4-bis (2-isocyanatoprop-2-yl) benzene (TMXDI), 1, 3-bis (isocyanatomethyl) benzene (XDI), and alkyl 2, 6-diisocyanatohexanoate (lysine diisocyanate) having a C1-C8-alkyl group.

In addition to the polyisocyanates mentioned above, it is also possible to use polyisocyanates having uretdiones, isocyanurates, urethanes, allophanates, biurets, imino groupsDiazinedione orModified diisocyanate with the diazinetrione structure and the functionality degree of more than or equal to 2, and a mixture of the components according to the proportion.

Hexamethylene diisocyanate, isophorone diisocyanate and mixtures of the foregoing diisocyanates are particularly preferred.

The polymer polyols have number-average molecular weights Mn in the range preferably from 400-8000g/mol, more preferably from 400-6000g/mol and particularly preferably from 600-3000g/mol, and preferably have OH functionalities of from 1.5 to 6, particularly preferably from 1.8 to 3 and very particularly preferably from 1.9 to 2.1.

The term "polymer" polyol here means, inter alia, that the polyol has at least two, more preferably at least three, repeating units linked together.

Such polymer polyols are the polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols and polyester polycarbonate polyols known in polyurethane coating technology. They can be used alone or in a mixture in the preparation of the polyurethanes of the invention.

The polymer polyol in the present invention is preferably polytetramethylene glycol polyether, polycarbonate polyol and a mixture thereof, and polytetramethylene glycol polyether is particularly preferred.

The hydroxy-functional compound having a molecular weight of 62 to 399mol/g may be a non-polymeric polyol having up to 20 carbon atoms, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, cyclohexanediol, 1, 4-cyclohexanedimethanol, 1, 6-hexanediol, neopentyl glycol, hydroquinone dihydroxyethyl ether, bisphenol A (2, 2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A (2, 2-bis (4-hydroxycyclohexyl) propane), trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, and any mixture thereof.

Also suitable are ester diols having the stated molecular weight range, such as α -hydroxybutyl epsilon-hydroxycaproate, ω -hydroxyhexyl gamma-hydroxybutyrate, β -hydroxyethyl adipate or bis (β -hydroxyethyl) terephthalate.

In addition, monofunctional isocyanate-reactive hydroxyl group-containing compounds having the molecular weight range described above can also be used. Examples of such monofunctional compounds are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, 2-ethylhexanol, 1-octanol, 1-dodecanol, 1-hexadecanol.

Suitable nonionically hydrophilizing agents are, for example, polyoxyalkylene ethers having isocyanate-reactive groups, such as hydroxyl, amino or thiol groups. Preference is given to monohydroxy-functionalized polyoxyalkylene polyether alcohols having (on a statistical average) from 5 to 70, preferably from 7 to 55, ethylene oxide units per molecule, which are obtainable by alkoxylation of suitable starter molecules in a manner known per se (for example in Ullmanns)der technischen Chemie, 4th edition, Volume19, Verlag Chemie, Weinheim pp.31-38). The abovementioned nonionically hydrophilicizing agents are pure polyoxyethylene ethers or mixed polyoxyalkylene ethers, where they contain at least 30 mol%, preferably at least 40 mol%, of ethylene oxide units, based on the total alkylene oxide units present.

Component A2) is preferably selected from primary or secondary amines and/or diamines. It comprises especially diamines.

Component a2), an amine having no ionic groups or ionogenic groups (e.g. anionically hydrophilicizing groups) may be used (component a2-I) below), and an amine having ionic groups or ionogenic groups (e.g. anionically hydrophilicizing groups, in particular) (component a2-II) below) may be used. Preference is given to reacting a mixture of component A2-I) and component A2-II).

For example, organic diamines or polyamines, such as 1, 2-ethylenediamine, 1, 2-and 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, isophoronediamine, isomer mixtures of 2, 2, 4-and 2, 4, 4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 4, 4-diaminodicyclohexylmethane, hydrazine hydrate, and/or dimethylethylenediamine can be used as component A2-I).

Furthermore, compounds which have secondary amino groups in addition to primary amino groups or OH groups in addition to amino groups (primary or secondary) can also be used as component A2-I). Examples thereof are primary/secondary amines, such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, alkanolamines, such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentanolamine.

In addition, monofunctional isocyanate-reactive amine compounds can also be used as component A2-I), for example methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isononyloxypropylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylaminopropylamine, diethyl (methyl) aminopropylamine, morpholine, piperidine, and suitable substituted derivatives thereof, amidoamines formed from diprimary amines and monocarboxylic acids, monoketimines (monoketimin) of diprimary amines, primary/tertiary amines, such as N, N-dimethylaminopropylamine.

As component A2-I), preference is given to using 1, 2-ethylenediamine, bis (4-aminocyclohexyl) methane, 1, 4-diaminobutane, isophoronediamine, ethanolamine, diethanolamine and diethylenetriamine.

Component A2) particularly preferably comprises at least one component A2-II). Suitable anionically hydrophilicizing compounds as component A2-II) preferably contain sulfonic acid or sulfonate groups, particularly preferably sodium sulfonate groups. Examples of such anionically hydrophilicizing agents are the salts of 2- (2-aminoethylamino) ethanesulfonic acid, ethylenediamine-propyl-or butyl-sulfonic acid, 1, 2-or 1, 3-propylenediamine- β -ethanesulfonic acid or taurine. Furthermore, the salts of Cyclohexylaminopropanesulfonic Acid (CAPS) of WO-A01/88006 can be used as anionic hydrophilicizing agents.

Particularly preferred anionic hydrophilicizing agents A2-II) are those which contain sulfonate groups as ionic groups and two amino groups, such as the salts of 2- (2-aminoethylamino) ethanesulfonic acid and 1, 3-propanediamine-. beta. -ethanesulfonic acid.

The polyurethanes of the present invention particularly preferably comprise at least one sulfonate group.

Optionally, the anionic groups in component A2-II) may also be carboxylate or carboxylic acid groups.

The preparation of the polyurethane dispersions can be carried out in one or more stages in homogeneous phase or, for multistage reactions, partly in dispersed phase. In this connection, all processes known in the art can be used, for example, prepolymer mixing processes, acetone processes or melt dispersion processes. Preferably, the acetone process is used.

In the production of the polyurethane prepolymers, the mass ratio of isocyanate groups to isocyanate-reactive groups (NCO index) is generally in the range from 1.05 to 3.5, preferably in the range from 1.1 to 3.0 and particularly preferably in the range from 1.1 to 2.5.

The solids content of the polyurethane dispersions preferably used for preparing the cosmetic compositions according to the invention is generally from 10 to 70% by weight, preferably from 30 to 65% by weight, particularly preferably from 40 to 60% by weight. The solids content is determined by heating the weighed sample to constant weight at 125 ℃. The solids content was calculated by reweighing the sample at constant weight.

Preferably, these polyurethane dispersions have less than 5% by weight, particularly preferably less than 0.2% by weight, based on the mass of the dispersion, of unbound organic amines. The content in the cosmetic composition is correspondingly low.

The polyurethane dispersion used for preparing the cosmetic composition of the present invention is preferably produced by Bayer materials scienceC1000，C1001，C1003，C1004 andC1008. it is particularly preferred thatC1004 andC1008。

the copolymers B) according to the invention comprise polymer units which are predominantly incorporated by the monomers B1) and the amphoteric monomers B2) described above and which are incorporated by means of further monomers up to 5% by weight, preferably up to 1% by weight, of the copolymer B). More preferred is a copolymer B) prepared from only the monomers B1) and the amphoteric monomers B2) described above.

The polymer units comprised by the copolymer B) of the present invention may also be introduced by pyrrolidone monomers.

Preferred monomers B1) are acrylic acid, methacrylic acid, acrylic acid C_1-20Alkyl esters and methacrylic acid C_1-20An alkyl ester.

Particularly preferably, the monomers B1) are selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, stearyl acrylate, stearyl methacrylate. Particularly preferred are acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate and stearyl methacrylate.

Preferred monomers B2 comprise (meth) acryloylalkylbetaines of formula B2-I and (meth) acryloyloxyalkyl-amine oxides of formula B2-II, wherein R is²And R³In each case independently of one another from methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, particularly preferably methyl.

The preferable monomer B2 further comprises a (methyl) acryloyl alkyl betaine shown in a formula B2-I and a (methyl) acryloyl alkyl amine oxide shown in a formula B2-II, wherein n is respectively selected from an integer of 1-5, preferably an integer of 1-3, and particularly preferably 2.

Preferred monomers B2 also include (meth) acryloylalkylbetaines of formula B2-I and (meth) acryloyloxyalkyl-amine oxides of formula B2-II, wherein R is¹Represents CH₃。

In a preferred embodiment, at least one amphoteric copolymer B) is synthesized from:

at least three monomers B1), the first monomer being selected from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate; the second monomer is selected from lauryl acrylate, lauryl methacrylate; and the third monomer is selected from octadecyl acrylate, octadecyl methacrylate. Meanwhile, B2) is a (meth) acryloylalkylamine oxide.

Amphoteric copolymers B) which meet the abovementioned conditions are known and include those produced by the company Mitsubishi under the trade designationZ-611，Z-612，Z-631，Z-632，Z-651，Z-711N andZ-731N, and the like, and those produced by LubrizolG-100，plus，Superhold andRSP, etc. Wherein,z-631 is preferred.

The cosmetic compositions according to the invention comprise, in addition to the polyurethane or polyurethane dispersion a) described above and at least one amphoteric copolymer B), a cosmetically acceptable medium, including in particular water and optionally cosmetically suitable solvents. Wherein the solid component or active ingredient in the polyurethane A) accounts for 0.1 to 10 percent of the weight of the cosmetic composition, and preferably 0.1 to 5 percent of the weight of the cosmetic composition. The solid component or active ingredient of the amphoteric copolymer B) is present in an amount of 0.1 to 20% by weight of the cosmetic composition. The weight of the solid component was determined by heating the weighed sample to a constant weight at 125 ℃. The weight of the solid component was calculated by reweighing the sample at constant weight.

The cosmetic composition according to the invention, wherein the weight ratio of the solid component of the polyurethane A) and the solid component of the amphoteric copolymer B) is from 1: 30 to 30: 1, preferably from 1: 10 to 10: 1, more preferably from 1: 3 to 3: 1.

The cosmetic compositions according to the invention preferably comprise from 0.1 to 30% by weight, based on the total weight of the composition, of the sum of the weights of the solid components of polyurethane A) and of amphoteric copolymer B) as described above.

As mentioned above, the cosmetically acceptable medium comprises, in particular, water and optionally cosmetically suitable solvents. Preferred solvents are aliphatic alcohols having C2-4 carbon atoms, such as ethanol, isopropanol, tert-butanol, n-butanol; polyols, such as propylene glycol, glycerol, ethylene glycol and polyol ethers; acetone; unbranched or branched hydrocarbons, such as pentane, hexane, isopentane and cyclic hydrocarbons, such as cyclopentane and cyclohexane; and mixtures thereof.

A very particularly preferred solvent is ethanol.

For low VOC type hair styling compositions, such solvents are preferably present in an amount of less than 80 wt%, more preferably less than 55 wt%, even more preferably less than 40 wt%, with the remainder being water, all based on the total weight of the composition.

In addition to the polyurethanes described above, the compositions according to the invention can include other suitable film formers which can also aid in the styling and styling of the hair.

The concentration of the one or more other film formers can be from 0 to 20 wt%, especially from 0 to 10 wt%, based on the total weight of the composition.

The film-forming agent may be selected from water-soluble or water-dispersible polyurethanes, other than the polyurethanes used in the present invention, polyureas, silicone resins and/or polyesters, and nonionic, anionic, amphoteric and/or cationic polymers and mixtures thereof.

The cosmetic composition according to the invention can furthermore advantageously comprise a thickener. Advantageous thickeners are: crosslinked or uncrosslinked acrylic or methacrylic acid homopolymers or copolymers; a natural thickening polymer; nonionic, anionic, cationic or amphoteric associative polymers, for example based on polyethylene glycols and their derivatives or polyurethanes; and crosslinked or uncrosslinked homopolymers or copolymers based on acrylamide or methacrylamide.

If thickeners are used, they are generally present in concentrations of from 0 to 2% by weight, preferably from 0 to 1% by weight, based on the total weight of the composition.

The cosmetic composition according to the invention may furthermore comprise a propellant gas. Here, it is advantageous to use the propellant gas in an amount of from 0 to 40% by weight and particularly preferably in a concentration of from 0 to 20% by weight, based on the total weight of the formulation.

Preferred propellant gases according to the invention are hydrocarbons such as propane, isobutane and n-butane, and mixtures thereof. However, according to the invention, compressed air, carbon dioxide, nitrogen dioxide and dimethyl ether, and mixtures of all these gases can also be used advantageously.

In addition, hair care actives and conventional additives can be used in the cosmetic compositions of the present invention. Such additives include silicones or silicone derivatives, wetting agents, humectants, emollients such as glycerin, glycols and phthalates and ethers, perfumes and fragrances, UV absorbers, dyes, pigments, and other colorants, anti-corrosion agents, neutralizers, antioxidants, anti-adhesion agents, binders and conditioners, antistatic agents, shine agents, preservatives, proteins and their derivatives, amino acids, vitamins, emulsifiers, surfactants, viscosity modifiers, thickeners and rheology modifiers, gelling agents, opacifiers, stabilizers, surfactants, sequestrants, complexing agents, pearlescers, reinforcing agents, fatty acids, fatty alcohols, triglycerides, botanical extracts, clarifying aids and film formers.

These additives are generally present in concentrations of about 0.001% to 15%, preferably 0.01% to 10% by weight, based on the total weight of the cosmetic composition.

The cosmetic compositions according to the invention, in particular the hair styling compositions, can be in the form of gels, emulsions, solutions or creams, for example in the form of styling mousses, styling fluids, hair sprays, styling gels, styling creams, aerosol mousses, etc. The cosmetic composition of the present invention can be applied to the keratin fibers such as hair by spraying or painting to achieve the shaping and/or styling effects.

A preferred embodiment of the hair styling composition according to the invention is in the form of a spray, which additionally comprises one or more of the following ingredients: cosmetically suitable solvents, aliphatic alcohols having 2 to 4 carbon atoms, preferably ethanol, polyols, acetone, unbranched or branched hydrocarbons, cyclic hydrocarbons and mixtures thereof, and propellant gases, such as hydrocarbons, compressed air, carbon dioxide, nitrogen dioxide, dimethyl ether, fluorocarbons and chlorofluorocarbons, preferably dimethyl ether and/or propane/butane mixtures.

The invention is illustrated by the following examples, which should not be construed as limiting. Unless otherwise indicated, all quantitative data, fractions and percentages are by weight or based on the total weight of the composition.

Examples

Raw materials and reagents

The examples and comparative examples of the present invention can be prepared as follows: EDTA Na was stirred at a stirring speed of 500-600rpm₂Adding propylene glycol and rheological agent into water until the mixture is uniformly dispersed; continuing with the separate addition of polyurethane A) according to the invention (A)C1004 orC1008) And amphoteric copolymers B), (B)Z-631) and continuously stirring to uniformly disperse the mixture; then AMP PC2000 was added until the pH was adjusted to around 6.5; finally, the preservative Liquid German Plus was added and stirred at 200-300rmp until uniformly dispersed. The resulting gel sample has a viscosity of > 10000, preferably 12000-15000mPa (measured at 25 ℃ with a rotation speed of 10rpm using a No. 63 measuring rotor)

The examples and comparative examples of the present invention all have the compositions as listed in the following table:

by adjusting the composition and ratio of the polyurethane A) to the ampholytic copolymer B), the comparative examples and examples shown in the following tables were obtained:

wherein wt% refers to the weight percent of the solid component of the composition based on the total weight of the gel sample. And the sum of the percentages by weight of the solid components in polyurethane A) and in amphoteric copolymer B) remains at 2% by weight.

The hair used in the following experiments was originated from asian hair provided by Rebecca hair manufacturing company, china, western china. All hair is healthy and is not bleached, dyed or otherwise chemically treated.

Evaluation experiment:

the prepared products are respectively smeared on the hair, after the hair is completely dried, the evaluation group consisting of five trained people scores each item, wherein 1 score is the lowest and the worst, and 10 scores are the best and the strongest. Since the scores are relative, there is no comparability between the scores of the respective groups.

Before evaluation of shampoo washability, each hair tress was rinsed with 1mL of a standard lotion (12% sodium lauryl sulfate solution) for 60 seconds and then rinsed with tap water at 25 ℃ for 30 seconds. After waiting for the tress to dry completely, it was visually inspected for the presence of polymer film residue.

TABLE 1 evaluation results of C1004 and Z-631 Components

TABLE 2 evaluation results of C1008 and Z-631 Components

From the above two evaluation experiments, it can be seen that the formulations using both polyurethane A) and ampholyte copolymer B) have significantly improved shampoo-removability, less residual white debris on the hair and comb, higher film hardness and elasticity, relative to the formulations using only polyurethane A).

Curl retention at high humidityLeave the experiment:

for the "curl retention" experiment, the hair was subjected to a standardized washing procedure. Hair softened in water for 15 minutes was shampooed for 2 minutes by using a 12 wt% sodium lauryl sulfate solution, rinsed thoroughly with warm water, dried on a cool air screen, and then conditioned at 22 ℃ and 55% relative humidity. While wet, 0.5cm wide strands were wound onto a spiral roller, blown dry for 35 minutes on a hot air screen, and then the polymer gel was spread evenly over the hair and allowed to dry thoroughly overnight.

The "curl retention" experiment was performed in a constant temperature and humidity cabinet with a relative humidity of > 90%. The temperature of the tank was maintained at 25 ℃. The prepared hair braid is suspended in the chamber at the same time, and a panel marked with height scales is arranged behind the back of the chamber. The length of the curl is read on the scale at certain times and compared to the starting length to give a percentage. Each data is an average of four hair braids.

TABLE 3 curl Retention test results for C1004 and Z-631 Components

TABLE 4 curl Retention test results for C1008 and Z-631 Components

From the two above experiments it can be seen that the formulations using both polyurethane a) and ampholytic copolymer B) have a significantly improved curl retention after a long time at high humidity, relative to the formulations using only ampholytic copolymer B).

Mechanical measurement experiment:

experiments designed by Stable Micro System Corporation (france) to measure the mechanical properties of membranes are well known in the art. The test uses a probe to contact the surface of a hair strand after the polymer gel has been applied and dried, and measures the stress of film formation while deforming the hair strand. From the curves of stress and deformation, the hardness, elasticity, etc. of the film can be calculated.

The model of the instrument used for this experiment was TA-XT Plus. The software parameters are listed in the following table:

pre-speed measurement	2mm/sec
		Test-speed	0.5mm/sec
After measurement-speed	1mm/sec
		Trigger force	2gram
Deformation of	4mm
		Number of cycles	10

The gel samples were applied evenly to the hair. The straightened hair was allowed to air dry overnight at 25 ℃ under 50% relative humidity. Each sample was applied to 5 tresses of hair and averaged after measurement.

TABLE 5 mechanical measurements of C1008 and Z-631 Components

The above experiments again demonstrate a significantly improved film hardness of the formulations using both polyurethane a) and ampholyte copolymer B) compared to the formulations using polyurethane a) alone.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing description, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description; and therefore any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims

1. A cosmetic composition comprises

a) At least one polyurethane a) obtainable by reacting one or more water-insoluble, non-water-dispersible isocyanate-functional polyurethane prepolymers a1) with one or more amino-functional compounds a 2); and

b) at least one amphoteric copolymer B).

2. The composition according to claim 1, wherein the amphoteric copolymer B) comprises at least two monomers B1) and B2), wherein

a) Monomer B1) is selected from any one or any mixture of acrylic acid, methacrylic acid, alkyl acrylate and alkyl methacrylate;

b) monomer B2) is amphoteric.

3. The composition of claim 2, wherein the amphoteric copolymer B) further comprises a pyrrolidone monomer.

4. The composition of claim 2, wherein monomer B2) is selected from (meth) acryloylalkylbetaines of formula B2-I:

and/or a (meth) acryloyloxyalkyl amine oxide represented by the formula B2-II:

wherein R is¹Optionally H or CH₃，R²And R³Each independently a straight or branched chain C₁-C₁₀An alkyl chain, and n represents an integer of 1 to 20.

5. The composition of claim 4, monomer B1) comprising monomers B1-I and B1-II, wherein

a) B1-I is any one or any mixture of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate or isopropyl methacrylate; and is

b) B1-II is octadecyl acrylate, octadecyl methacrylate, or a mixture thereof.

6. The composition of claim 4, monomer B2) being a methacryloylethylamine oxide of formula B2-II, wherein R is¹、R²And R³Are all CH₃And n is 2.

7. The composition of any of claims 1 to 6, wherein amino-functional compound A2) is optionally a primary and/or secondary amine and/or diamine.

8. The composition of claim 7, wherein the amino-functional compound a2) comprises at least one diamine.

9. The composition of claim 7, wherein amino-functional compound a2) comprises amino-functional compound a2-I having no ionic groups or ionogenic groups and amino-functional compound a2-II having ionic groups and/or ionogenic groups.

10. The composition of claim 9, wherein a2-I is a diamine having no ionic groups or ionogenic groups.

11. The composition of claim 7, wherein prepolymer a1) is obtainable by reacting one or more selected from polyether polyols, polycarbonate polyols, polyether polycarbonate polyols and/or polyester polyols with one or more polyisocyanates.

12. The composition of claim 11 wherein the polyisocyanate comprises hexamethylene diisocyanate and/or isophorone diisocyanate.

13. The composition of claim 1, wherein the polyurethane a) contains at least one sulfonic acid and/or sulfonate group.

14. The composition of claim 13, wherein the sulfonate group is a sodium sulfonate group.

15. The composition of claim 7 wherein the solid component of polyurethane a) is present in an amount of from 0.1% to 20% by weight of the cosmetic composition.

16. The composition of claim 15 wherein the solids component of ampholyte copolymer B) is present in an amount of from 0.1% to 20% by weight of the cosmetic composition.

17. The composition as claimed in claim 16, wherein the weight ratio of polyurethane a) to ampholyte copolymer B) is from 1: 30 to 30: 1.

18. The composition of claim 17, wherein the weight ratio of polyurethane a) to ampholyte copolymer B) is from 1: 10 to 10: 1.

19. The composition of claim 18, wherein the weight ratio of polyurethane a) to ampholyte copolymer B) is from 1: 3 to 3: 1.

20. The composition of claim 16 wherein the sum of the weights of polyurethane a) and ampholyte copolymer B) is from 0.1% to 30% by weight of the total cosmetic composition.

21. The composition according to claim 16, further comprising any one or any mixture of other hair styling polymers, thickeners, pigments, surfactants, preservatives, oils, waxes, uv filters.

22. A cosmetic composition comprises

a) At least one polyurethane a) obtainable by reacting one or more water-insoluble, non-water-dispersible isocyanate-functional polyurethane prepolymers a1) with one or more amino-functional compounds a 2);

wherein prepolymer a1) is obtainable by reacting one or more polyols selected from the group consisting of polyether polyols, polycarbonate polyols, polyether polycarbonate polyols and/or polyester polyols with hexamethylene diisocyanate and/or isophorone diisocyanate; amino-functional compound a2) comprises both amino-functional compound a2-I having no ionic group or ionogenic group and amino-functional compound a2-II having an ionic group and/or ionogenic group;

b) at least one amphoteric copolymer B) comprising monomers B1) and B2);

wherein the monomer B1) is selected from any one or any mixture of acrylic acid, methacrylic acid, alkyl acrylate and alkyl methacrylate; monomer B2) is a methacryloylethylamine oxide of formula B2-II, wherein R is¹、R²And R³Are all CH₃And n is 2.

23. The composition of claim 22 wherein the solid component of polyurethane a) is present in an amount of from 0.1% to 20% by weight of the cosmetic composition.

24. The composition of claim 23 wherein the solids component of ampholyte copolymer B) is present in an amount of from 0.1% to 20% by weight of the cosmetic composition.

25. The composition of claim 24, wherein the weight ratio of polyurethane a) to ampholyte copolymer B) is from 1: 30 to 30: 1.

26. The composition of claim 25, wherein the weight ratio of polyurethane a) to ampholyte copolymer B) is from 1: 10 to 10: 1.

27. The composition of claim 26 wherein the weight ratio of polyurethane a) to ampholyte copolymer B) is from 1: 3 to 3: 1.

28. The composition of claim 24 wherein the sum of the weights of polyurethane a) and ampholyte copolymer B) is from 0.1% to 30% by weight of the total cosmetic composition.

29. Use of a cosmetic composition according to claim 1 or 22 for shaping and/or styling keratin fibres.

30. A method for shaping and/or styling keratin fibers, comprising applying the cosmetic composition of claim 1 or 22 to the keratin fibers.