WO1995021602A1

WO1995021602A1 - Polymer-containing hair care products

Info

Publication number: WO1995021602A1
Application number: PCT/EP1995/000309
Authority: WO
Inventors: Joachim Conradi; Ulrich Eicken; Winfried Emmerling; Annedore Niemann; Ludwig Schieferstein
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1994-02-08
Filing date: 1995-01-30
Publication date: 1995-08-17
Also published as: DE4403952A1

Abstract

Polyoxazoline-containing hair care products are characterised by good fixing properties, reduced residual viscosity and pronounced anti-static effect. In addition, they can be easily sprayed and may be easily removed from the hair by brushing and washing.

Description

"Hair treatment agents with polymers"

The invention relates to hair treatment compositions with polyoxazolines.

An appealing looking hairstyle is now generally regarded as an indispensable part of a well-groomed exterior. Due to current fashion trends, hairstyles are always considered chic, which can only be built up with many hair types using certain setting agents or maintained for a longer period of time.

These setting agents can be incorporated into conventional hair cleaners or conditioners. In many cases, however, it is advantageous to use them in the form of special agents such as hair fixers or hair sprays.

A number of polymeric compounds, such as, for example, polyvinylpyrrolidones and vinyl acetate-vinylpyrrole don copolymers, have proven successful as setting agents.

However, there have recently been a number of developments in the hair cosmetics field which have created a need for polymers with special, appropriately adapted properties.

An example of such a development is the transition from fluorochlorohydrocarbons as blowing agents (and solvents) to lower alkanes, dimethyl ether, carbon dioxide, nitrogen and air. A further development is the transition from solvent-based agents to water-based agents. Furthermore, the formulation as a pump spray also places special demands on the polymers in order to achieve acceptable spray behavior.

Finally, perfume-free formulations or formulations for perfuming by the consumer are also increasingly desired, so that odorless behavior of the individual components is becoming increasingly important. It has now been found that polyoxazolines are outstandingly suitable as active ingredients for hair treatment agents. In formulations with dimethyl ether, the polyoxazolines can be distributed very homogeneously. The formulations are stable in storage and show good spray characteristics when sprayed. The formulations show good setting properties with low residual tack and can also be used as finishing agents due to their antistatic effect. After all, they can easily be removed from the hair by washing or brushing.

The invention therefore relates to hair treatment compositions comprising conventional cosmetic ingredients which contain a polyoxazoline.

Polyoxazolines are known from the literature. They can be obtained by cationic polymerization of appropriate 4,5-dihydro-1,3-oxazoles with ring opening. Procedures in this regard can be found, for example, in German patent applications 12 06 585, 15 70 213 and 19 04 540. A further process for the production of polyoxazolines can be found in the German patent application P 44 03 953.0 filed on the same day, to which express reference is made.

Polyoxazolines, which essentially consist of one another, have proven to be particularly advantageous

25-99.9 mol% of monomer units (A) of the formula (I),

in which R ^{1 is} hydrogen, an alkyl or alkenyl radical having 1 to 3 carbon atoms or a unit R3- [0-CH2-CH2] χ-, in which R3 is a methyl, ethyl or propyl group and x is a number of 1 to 5, or a mixture of such residues,

0.1-50 mol% of monomer units (B) of the formula (II),

in which R ^ represents a linear or branched alkyl or alkenyl radical, cycloalkyl or cycloalkenyl radical having 4 to 22 carbon atoms, an optionally alkyl or alkenyl-substituted, aromatic or heterocyclic radical having 5 to 22 carbon atoms or a mixture of such radicals, and

0 - 50 mol% of monomer units (C) which are formed by copolymerization with ethylene oxide, propylene oxide, vinyl ethers, oc-methylstyrene, isobutylene, ethylene, propylene or 2-Cι_i8-alkyl-oxazines,

with the proviso that the amount of monomer units (A) is not less than the amount of monomer units (B).

The term "essentially assemble" should be understood to mean that only the corresponding monomers are used. If the polymers have further building blocks, they are either impurities from the polymers or start or termination reagents.

Both in the monomer units of type (A) and in the monomer units of type (B), it has proven advantageous that a group -CH2-CH2-N- forms the main polymer chain. Nevertheless, it is possible, according to the invention, to also use monomers in which these carbon atoms each have alkyl groups, in particular methyl groups, as substituents instead of one or both hydrogen atoms.

The majority of the oxazoline monomer units are the monomers of type (A). R ¹ can be hydrogen, a methyl, ethyl, n-propyl, iso-propyl or allyl group, or a mixture of these Groups stand. Monomer units in which R ^{1 represents} a methyl or an ethyl group are particularly preferred. The monomer in which R * represents an ethyl group is very particularly preferred. Furthermore, Rl can be used for a Group R3- [0-CH2-CH2] χ-, in which R ^ is a methyl, ethyl or propyl group, x is a number from 1 to 5.

Preferred groups for which R ^ can stand are nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, heptadecenyl, cyclohexyl, phenyl and benzyl groups. To the extent that starting materials which originate from natural fats and oils have been used for the synthesis of the oxazolines, appropriate mixtures of alkyl groups, such as occur in the carboxylic acids of the fats and oils mentioned, can be preferred. In special cases, monomer units may be preferred which carry benzyl or phenyl groups as substituents R.sup.1.

Polyoxazolines which have only monomer units of type (A) and (B) are preferred according to the invention. However, it has been found that such polymers also have satisfactory properties according to the invention in which up to 50 mol%, in particular up to 20 mol%, of the monomers are of a different, nonionic type of monomer (C). Preferred nonionic co-monomers are ethylene oxide, propylene oxide, vinyl ether, α-methylstyrene, isobutylene, ethylene, propylene and 2-Cι_i8-alkyl-oxazines.

The monomer units (A), (B) and optionally (C) can occur in the polyoxazolines according to the invention both statistically distributed and in the form of blocks of the respective monomer units. While a statistical distribution has proven advantageous for units (A) and (B), it may be preferred to position units (C) in block form at the ends of the polymer chains.

The polyoxazolines which can be used according to the invention preferably have average molecular weights between 1,000 and 1,000,000. Polyoxazolines with average molecular weights between 2,000 and 50,000 have proven to be particularly suitable according to the invention.

The skilled worker is familiar with the possibilities of obtaining molecular weights in a desired range during polymer synthesis. In the present polyoxazolines, this can be done, for example, by choosing the starter, for example methyl tosylate. Polymers with 70-99 mol% of monomers (A), 1-30 mol% of monomers (B) and 0-20 mol% of monomers (C) have proven to be particularly suitable according to the invention.

The hair treatment compositions according to the invention contain the polyoxazoline, depending on the type of hair treatment composition which is not subject to any restrictions, preferably in amounts of 0.05 to 15% by weight, in particular 0.1 to 8% by weight, based on the total Medium.

The polyoxazolines are preferably the only synthetic polymers in the hair treatment compositions according to the invention. If desired, however, these can also contain further nonionic, cationic, anionic, zwitterionic and ampholytic polymers.

The other constituents of the hair treatment compositions according to the invention depend on the type of hair treatment composition. In principle, the polyoxazolines are advantageous active ingredients for all known types of hair treatment compositions, such as Hair fixers, hair sprays, blow-dry waves, hair shampoos, hair rinses, hair conditioners, hair treatments, permanent waving agents, and hair colorants.

It is preferred to select such agents that are formulated on an aqueous basis. Aqueous basis in the sense of this application means that in addition to water other solvents only in amounts up to max. 40 wt .-%, based on the total agent, are included. In particular, it may be preferred to use solvents such as lower alcohols, i.e. e.g. Ethanol or isopropanol, to be used only in amounts of less than 20% by weight, in particular less than 10% by weight, or not at all in the agents according to the invention.

Also preferred are agents which contain ethyl ether as a component, in particular in amounts of 10% by weight and more.

Preferred hair treatment compositions according to the invention are those which remain on the hair after use. These are, in particular, hair fixers, hair sprays and blow dryer waves. Such agents can also be formulated with the aid of a propellant as a foam aerosol. Further components of the agents according to the invention can be, for example:

anionic surfactants, such as, for example, fatty alkyl sulfates and ether sulfates, cationic surfactants, such as, for example, quaternary ammonium compounds, zwitterionic surfactants, such as, for example, betaines, ampholytic surfactants, nonionic surfactants, such as, for example, alkylpolyglycosides and ethoxylated fatty alcohols, cationic polymers such as quaternized cellulose ethers, polysiloxanes quaternary groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, dimethylaminoethyl methacrylate-vinylpyrrolidone copolymers quaternized with diethyl sulfate, vinylpyrrolidone-methoimidazolinium chloride copolymers and quaternized polyvinyl alcohol-vinyl acrylate / vinyl acrylate molybdate / Methyl vinyl ether / maleic anhydride copolymers and their esters as well as uncrosslinked and polyols crosslinked polyacrylic acids, zwitterionic and a photere polymers such as wise acrylamido propyl trimethylammonium chloride / acrylate copolymers, octylacrylamide / methy1-methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropylimethacrylate copolymers, nonionic polymers such as polyvinylpyrrolidone, vinyl pyrrolidone / vinyl acetate copolymers and cellulose copolymers such as cellulose and maleic acid, hair-conditioning compounds such as phospholipids, for example soy lecithin, egg lecithin and cephalins, and also silicone oils, protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and wheat protein hydrolysates, their condensation products with fatty acids and also quaternized Protein hydrolyzates, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, dyes, Anti-dandruff agents such as Piroctone Ola ine and Zink Omadine, other substances for adjusting the pH value,

Active ingredients such as panthenol, allantoin, pyrrolidone carboxylic acids and their salts, plant extracts and vitamins, light stabilizers,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, fats and waxes such as walrus, beeswax, montan wax, paraffins and fatty alcohols, fatty acid alkanolamides,

Complexing agents such as EDTA, NTA and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and also primary, secondary and tertiary phosphates, opacifiers such as latex,

Pearlescent agents such as ethylene glycol mono- and distearate, blowing agents such as propane-butane mixtures, N2O, CO2 and air as well as antioxidants, direct dyes, so-called coupler and developer components as oxidation dye precursors,

Reducing agents such as Thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thio malic acid and α-mercaptoethanesulfonic acid, oxidizing agents such as hydrogen peroxide, potassium bromate and sodium bromate.

The invention also relates to the use of the compositions according to the invention for the treatment of keratin fibers, in particular hair.

The following examples are intended to explain the invention in more detail. Examples

1. Manufacturing examples

1.1 poly-ethyloxazoline-co-phenyloxazoline (5: 1)

3.47 g (0.035 mol) of 2-ethyloxazoline, 1.03 g (0.007 mol) of 2-phenyloxazoline and 1.56 g (0.0084 mol) of methyl tosylate were combined under a nitrogen atmosphere and heated to 160.degree. With stirring, 65.83 g (0.665 mol) of 2-ethyloxazoline and 19.55 g (0.133 mol) of 2-phenyloxazoline were then added dropwise in parallel within 95 minutes. The copolymer obtained had an average molecular weight of 11,000.

1.2 poly-ethyloxazoline-co-undecyloxazoline (15: 1)

22.28 g (0.225 mol) of 2-ethyloxazoline, 3.38 g (0.015 mol) of 2-undecyloxazoline and 9.0 g (0.048 mol) of methyl tosylate were combined under a nitrogen atmosphere and heated to 160.degree. 423.22 g (4.275 mol) of 2-ethyloxazoline and 64.12 g (0.285 mol) of 2-undecyloxazoline were then added dropwise in parallel over the course of 60 minutes with stirring. The mixture was then stirred at 160 ° C. for a further 30 minutes. The copolymer obtained had an average molecular weight of 11,000.

2. Application properties

The following polyoxazolines were examined:

Monomer 1 Monomer 2 Molar ratio Average glass temperature

Monomer 1: Monomer 2 molar mass [° C]

01 2-ethyloxazoline 2-nonyloxazoline 10: 1 10700 37-40

02 2-ethyloxazoline 2-undecyloxazoline 15: 1 10800 38-49

03 2-ethyloxazoline 2-phenyloxazoline 15: 1 10,200 72-75

04 2-ethyloxazoline 2-phenyloxazoline 5: 1 10700 69-73 O

05 2-ethyloxazoline 2-phenyloxazoline 5: 1 2700 60-62 I.

Luviskol ^ VA 64, a product of BASF, was investigated as comparative substance VI. This substance is a vinyl acetate-vinyl pyrrolidone copolymer in a ratio of 40:60

The following mix types were produced:

Ml: mixture of 60% (63% water / 27% ethanol / 10% polymer) and

40% dimethyl ether

M2: mixture of 70% (90% water / 10% polymer)

30% dimethyl ether

Relative information such as "Good" or "medium" each refer to the subjective comparison with commonly used polymers.

The following properties were examined:

System investigated 01 / Ml 01 / M2 02 / Ml 02 / M2

Compatibility with the clearly soluble not clearly clearly soluble clearly soluble blowing agent dimethyl ether soluble

Spray behavior good good good

Appearance of the film transparent transparent

I y

Residual stickiness low low medium

Odor neutral neutral neutral neutral

Investigated system 03 / M2 04 / M2

Compatibility with the blowing agent dimethyl ether

- Clearly soluble at room temperature Clearly soluble

- Clearly soluble at -10 ° C Clearly soluble

Spray behavior good good

Appearance of the film transparent transparent

firming effect on hair medium medium

Remaining stickiness on the hair stronger medium

Can be brushed out of the hair medium medium

Washability from the hair is good

Odor neutral neutral

System investigated: 03 / Ml 04 / Ml 05 / Ml VI / Ml

Compatibility with the blowing agent dimethyl ether

- at room temperature clearly soluble clearly soluble clearly soluble clearly soluble

- at -10 ° C clearly soluble clearly soluble clearly soluble clearly soluble

Spray behavior g t (+) good good good

Appearance of the film transparent transparent transparent transparent ω setting effect on hair medium medium somewhat weaker medium

Residual stickiness on the hair somewhat larger medium somewhat larger medium

Brushability from the hair good good good good

Washability from the hair good good good good

static charge of the hair low low low large

3. Formulation examples

All quantities are in% by weight.

3.1. Spray strengthener

Ethanol 20.0

Polyoxazoline 03 5.0

Panthenol 1.0

Perfume oil 0.2

Water ad 100

3.2. Pump spray

Ethanol 30.0

Polyoxazoline 04 8.0

Nutrilan ^R ll 1.0

Perfume oil q.s.

Water ad 100

Collagen hydrolyzate (approx. 39% active substance; CTFA name: hydrolyzed collagen) (HENKEL)

Claims

claims

1. Hair treatment agent containing, in addition to conventional cosmetic components, a polyoxazoline, characterized in that the polyoxazoline is composed essentially of

25-99.9 mol% of monomer units (A) of the formula (I),

in the R1 for hydrogen, an alkyl or alkenyl radical having 1 to 3 carbon atoms or a unit R3- [0-CH2-CH2] χ-, in which R3 is a methyl, ethyl or propyl group and x is a number from 1 to 5, or a mixture of such residues,

0.1-50 mol% of monomer units (B) of the formula (II),

in which R ^{2 represents} a linear or branched alkyl or alkenyl radical, cycloalkyl or cycloalkenyl radical with 4 to 22 carbon atoms, an optionally alkyl or alkenyl-substituted, aromatic or heterocyclic radical with 5 to 22 carbon atoms or a mixture of such radicals, and

- 0 - 50 mol% of monomer units (C) which are formed by copolymerization with ethylene oxide, propylene oxide, vinyl ethers, α-methylstyrene, isobutylene, ethylene, propylene or 2 -C 8 alkyl alkylazines,

2. Hair treatment composition according to claim 1, characterized in that the polyoxazoline is composed essentially of

70-99 mol% of monomer units (A),

1 - 30 mol% of monomer units (B) and

0-20 mole% monomer units (C).

3. Hair treatment composition according to claim 1 or 2, characterized in that Rl represents an ethyl group, R ^{2 is} a saturated alkyl radical having 8 to 18 carbon atoms, a phenyl or a benzyl group.

4. Hair treatment composition according to claim 1 or 2, characterized in that Rl represents an ethyl group and R ^{2 is} a phenyl or a Ben¬ zylgruppe.

5. Hair treatment agent according to one of claims 1 to 4, characterized ge indicates that the polyoxazoline in amounts of 0.05 to 15 wt .-%, in particular 0.1 to 8 wt .-%, based on the total agent ent ¬ hold.

6. Hair treatment composition according to one of claims 1 to 5, characterized ge indicates that it is formulated on an aqueous basis and other solvents only in amounts up to max. 40% by weight, based on the total agent, are contained.

7. Hair treatment composition according to one of claims 1 to 6, characterized in that it contains at least 10 wt .-% dimethyl ether.

8. Hair treatment composition according to one of claims 1 to 7, characterized in that it remains on the hair after use.

9. Hair treatment composition according to one of claims 1 to 8, characterized ge indicates that it is formulated as a foam aerosol.

10. Use of an agent according to one of claims 1 to 9 for the treatment of hair.