DE20000871U1 - Hair care emulsion - Google Patents

Description

t + m

Hair care emulsion

The present invention relates to a hair care product in the form of a water-in-oil emulsion with improved hair conditioning properties.

It has been known for decades that hair conditioning agents of various kinds can be used. They usually contain cationic active ingredients, in particular quaternary long-chain ammonium compounds, and/or polymers with quaternary nitrogen atoms and are used in particular as solutions, oil-in-water emulsions, gels or lotions, which can also be used as aerosols or pump sprays.

Corresponding compositions, which either remain in the hair after application or can be washed out, are described, for example, in the monograph by K. Schrader, Fundamentals and Recipes of Cosmetics, 2nd edition, (Hüthig Buch Verlag, 1989) on pages 722 to 781 under the keyword "hair after-treatment products".

Despite their diversity, these products still have room for improvement in terms of their application properties.

It has now been found, and this is the subject of the present invention, that an optimal conditioning hair after-treatment agent consists of a water-in-oil emulsion which contains at least one water-soluble polymer in the aqueous phase and at least one poorly water-soluble plant protein hydrolysate in the fat or oil phase.

This product not only gives the hair shine, fullness and volume, a full grip, resilience and improved wet and dry combability, but also a long-lasting fixing effect that can be regulated by the polymer/protein hydrolysate ratio, but also does not exhibit any stickiness or hygroscopicity on the hair, which is otherwise often found with such products.

The poorly soluble plant protein hydrolysate obviously remains almost exclusively in the oil or fat phase of the W/O emulsion and does not diffuse into the water phase.

The term "poorly water-soluble plant protein hydrolysate" refers to one whose clear solubility in water at 20 ⁰ C is less than 0.5 g/100 ml H2O, preferably less than 0.3 g/100 ml H2O.

The molecular weight of this plant protein hydrolysate is preferably between about 10,000 and about 500,000, in particular about 15,000 to 400,000, particularly preferably about 25,000 to 250,000 g/mol.

Suitable plant protein hydrolysates include those from soybean protein, almond protein, wheat protein and other cereal proteins, potato protein and especially pea protein, Pisum sativum.

The suitable amount of the plant protein hydrolysate is about 0.1 to 5, in particular about 0.25 to about 2.5 wt.%, calculated on the total W/O emulsion.

Suitable water-soluble polymers which are present in the water phase of the W/O emulsion according to the invention have also been known in principle for a long time.

Their amount is preferably about 0.25 to 10, in particular about 0.5 to about 7.5, especially about 1 to 5 wt.%, calculated on the total composition of the emulsion.

Preference is given to nonionic polymers such as water-soluble vinylpyrrolidone polymers, e.g. vinylpyrrolidone mono- or copolymers, in particular with vinyl acetate.

Suitable vinylpyrrolidone polymers are, for example, the products known under the trade name "Luviskol®", for example the homopolymers "Luviskol® K 30, K QQ. and K 9ß" as well as the water-soluble copolymers of vinylpyrrolidone

i W" Vi ü ii W i ':"': :'''i U .!.

and vinyl acetate, which are sold under the trade name "Luviskol® VA 55 or VA 64" by BASF AG.

Other suitable non-ionic polymers are vinylpyrrolidone/vinyl acetate/vinyl propionate copolymers such as "Luviskol® VAP 343", vinylpyrrolidone/(meth)acrylic acid ester copolymers and chitosan derivatives.

Instead of or in addition to the non-ionic polymers, cationic and/or anionic and/or amphoteric polymers in particular can be used as conditioning polymers in the amounts mentioned.

Preferred conditioning cationic polymers are the well-known quaternary cellulose derivatives of the "Polymer JR" type and quaternized homo- and copolymers of dimethyldiallylammonium chloride, as are sold under the trade name "Merquat®", quaternary vinylpyrrolidone copolymers, in particular with dialkylaminoalkyl (meth)acrylates, as are known under the name "Gafquat®", copolymers of vinylpyrrolidone and vinylimidazolinium methochloride, which are sold under the trade name "Luviquat®", polyamino-polyamide derivatives, for example copolymers of adipic acid-dimethylaminohydroxypropyldiethylenetriamine, as are sold under the name "Cartaretine® F", as well as bisquaternary long-chain ammonium compounds of the urea structure described in US Pat. No. 4,157,388, which are sold under the trade name "Mirapol® A 15" are available.
In this context, reference is also made to the cationic polymers mentioned in DE-OSs 25 21 960, 28 11 010, 30 44 738 and 32 17 059 as well as the products described in EP-A 337 354 on pages 3 to 7. Mixtures of different cationic polymers can also be used.
The cationic polymers also include the quaternization products of graft polymers of organopolysiloxanes and polyethyloxazolines described in EP-A 524 612 and EP-A 640 643.

Amphoteric polymers which are used alone or in a mixture with at least one other cationic, non-ionic or anionic polymer are in particular copolymers of N-octylacrylamide, (meth)acrylic acid and

tert-butylaminoethyl methacrylate of the type "Amphomer®"; copolymers of methacryloylethyl betaine and alkyl methacrylates of the type "Yukaformer®", e.g.
Butyl methacrylate copolymers "Yukaformer® Am75"; copolymers of monomers containing carboxyl groups and sulfone groups, e.g. (meth)acrylic acid and itaconic acid, with monomers containing basic groups, in particular amino groups, such as mono- or dialkylaminoalkyl(meth)acrylates or mono- or dialkylaminoalkyl(meth)acrylamides; copolymers of N-octylacrylamide, methyl methacrylate, hydroxypropyl methacrylate, N-tert-butylaminoethyl methacrylate
and acrylic acid as well as the copolymers known from US-A 3,927,199.

Suitable anionic polymers are vinyl alkyl ether, in particular methyl vinyl ether/maleic acid copolymers, which are formed by hydrolysis of vinyl ether/maleic anhydride copolymers and are sold under the trade name "Gantrez® AN or ES". These polymers can also be partially esterified, for example "Gantrez® ES 225", the ethyl ester of an ethyl vinyl ether/maleic acid copolymer, or the butyl or isobutyl ester of the same.

Other suitable anionic polymers are in particular vinyl acetate/crotonic acid or vinyl acetate/vinyl neodecanoate/crotonic acid copolymers of the "Resyn®" type; sodium acrylate/vinyl alcohol copolymers of the "Hydagen® F" type, sodium polystyrene sulfonate, e.g. "Flexan® 130"; ethyl acrylate/acrylic acid/N-tert-butylacrylamide copolymers of the "Ultrahold®" type; vinylpyrrolidone/vinyl acetate/itaconic acid copolymers, acrylic acid/acrylamide copolymers or sodium salts thereof of the "Reten®" type; etc.

In addition to the two essential ingredients, the agents according to the invention can also contain other conditioning water-soluble protein hydrolysates and polypeptides, e.g. keratin hydrolysates, collagen hydrolysates of the "Nutrilan®" type or elastin hydrolysates and, in particular, vegetable, optionally cationized protein hydrolysates, e.g. "Gluadin ^R ".

Examples of such substances include complexing agents, dyes, preservatives,
pH regulators, viscosity regulators such as inorganic salts, fragrances, pearlescent agents, thickeners, humectants, vegetable and animal oils such as jojoba oil, fatty acid esters such as isopropyl myristate, ethyl palmitate, lecithin and its derivatives, etc.

Finally, known polysiloxanes can also be used as conditioning agents in the hair care emulsions according to the invention, preferably in the oil or fat phase. The preferred proportion thereof is between about 0.5 and about 5, in particular 1 to 3% by weight of the total composition.

Both highly volatile and non-volatile cyclic or linear polysiloxanes are suitable, e.g. the silicone oils known under the trivial names "dimethicone" or "phenyldimethicone" and "cyclomethicone", as well as, for example, the silicone derivatives described in EP-A 398 177, which are used there in combination with alkyl polyglucosides in liquid detergent compositions.

A further preferred component in the agents according to the invention are plant extracts in an amount of about 0.01 to about 10, preferably 0.1 to 7.5, in particular 0.5 to 5% by weight, calculated as the dry residue thereof based on the total amount of the agent, which are preferably present in the aqueous phase of the W/O emulsion according to the invention.

Suitable, known aqueous (e.g. steam distilled), alcoholic or aqueous-alcoholic plant extracts are in particular extracts of leaves, fruits, flowers, roots, bark or stems of aloe, pineapple, artichoke, arnica, avocado, valerian, bamboo, henbane, birch, nettles, echinacea, ivy, angelica, gentian, ferns, spruce needles, cinquefoil, ginseng, broom, oats, rose hips, witch hazel, hay flowers, elderberry, hops, coltsfoot, currants, camomile, carrots, chestnuts, clover, burdock roots, coconut, corn, linden blossom, lily of the valley, seaweed, lemon balm, mistletoe, passion flowers, ratanhia, marigolds, rosemary, horse chestnuts, hawthorn, sage, horsetail, yarrow, primroses, dead nettles, Thyme, walnuts, vine leaves, hawthorn, etc.

&idigr; i ti

Suitable commercial products are, for example, the various "Extrapone ^R ", "Herbasol ^R ", "Sedaplant ^R " and "Hexaplant ^R ". Extracts and their production are also described in "Hager's Handbook of Pharmaceutical Practice", 4th edition.

The aftertreatment agents according to the invention can preferably also contain at least one cationic surfactant, such as a quaternary ammonium compound, which also has a conditioning effect.

Suitable long-chain quaternary ammonium compounds, which can be used alone or in mixtures, are for example cetyltrimethylammonium chloride,
Dimethyldicetylammonium chloride, trimethylcetylammonium bromide,
stearyltrimethylammonium chloride, dimethylstearylbenzylammonium chloride,
Benzyltetradecyldimethylammonium chloride Dimethyl dihydrogenated tallow ammonium chloride,
Laurylpyridinium chloride, Lauryldimethylbenzylammonium chloride,
Behenyltrimethylammonium chloride, Lauryltrimethylammonium chloride,
Tri-(oligooxyethl)alkylammonium phosphate, cetylpyridinium chloride,
etc. The quaternary ammonium salts disclosed in EP-A 472 107 are also very suitable.

In principle, all quaternary ammonium compounds as listed in the currently valid “CTFA International Cosmetic Ingredient Dictionary” under the trivial name “Quatemium” can be used.

Their proportion is preferably about 0.5 to 10, in particular about 1 to 7.5
% by weight, calculated on the total composition.

Particularly suitable long-chain ammonium compounds are esterquats of the general formula (I)

^R3
I
[R ¹ -CO -[EO] -OCH ₂ CH ₂ -N-CH ₂ CH ₂ O-[EO] -COR ² ] Y"

^R4 (I)

in which R ¹ and R ² represent an optionally hydroxy-substituted C

or alkenyl group, R ³ and R ⁴ represent a Ci-C3-alkyl group or a
Group-CH ₂ -CH ₂ -O-[EO] ₂ H and x,y and &zgr; for 0 to 5 and Y" for a
Anion.

A particularly preferred compound of formula I within the scope of the invention is one in which the radicals R ¹ and R ² each represent an oleyl group or a C ₁₂ -C 18 alkyl group, the radical R ³ represents a methyl group and the radical R ⁴ represents a group -CH ₂ -CH ₂ -O-[EO] ₂ -H.

The anion Y" is preferably a halide such as Cl" or Br', a lower alkyl sulfate, e.g. methosulfate and ethosulfate, or an alkyl phosphate, but of course other radicals can also be used.

These compounds are known per se and are sold under the trade names "Schercoquat*", "Dehyquart ^R F30" and "Tetranyl ^R ".

The use of these compounds, so-called "esterquats", in hair care products is known per se and is described, for example, in WO-A 93/10748, WO-A 92/06899 and WO-A 94/16677, where, however, there is no reference to the combination according to the invention and its advantageous properties.

Amidoquats of the general formula (II) are also suitable

^R3

R ¹ -C-N-CH ₂ CH ₂ -N -CH ₂ CH ₂ -NCR ²
OH R ⁴ HO

(II)

in which R ¹ and R ² each represent an optionally hydroxy-substituted C ₈ -C ₂₂ alkyl
or alkenyl group, R ³ and R ⁴ represent a Ci-Cß-alkyl group or a group
-CH ₂ -CH ₂ -O-[EO] _x -H, and &khgr; stands for O to 5, Y" stands for an anion.

The aftertreatment agents according to the invention contain oils and fats in the fat phase.

Suitable fats and oils, which also include waxes, are particularly natural oils such as avocado oil, coconut oil, palm oil, sesame oil, peanut oil, sperm oil, • .·:::::::: ."· _: '

Sunflower oil, almond oil, peach kernel oil, wheat germ oil, macadamia nut oil, evening primrose oil, jojoba oil, castor oil, or olive or soybean oil, lanolin and its derivatives, as well as mineral oils such as paraffin oil and Vaseline.
Synthetic oils and waxes include silicone oils, polyethylene glycols,
Etc.

Other suitable hydrophobic components are in particular fatty acid esters such as isopropyl myristate, palmitate, stearate and isostearate, oleyl oleate, isocetyl stearate, hexyl laurate, dibutyl adipate, dioctyl adipate, myristiyl myristate, oleyl erucate, polyethylene glycol and polyglyceryl fatty acid esters such as PEG-7-glyceryl cocoate, cetyl palmitate, etc.

These hydrophobic components are preferably contained in the post-treatment compositions according to the invention in a total amount of about 5 to about 50, in particular about 7.5 to 35, especially about 10 to 25 wt.%, calculated on the total composition of the emulsion.

The aftertreatment agents according to the invention can also contain long-chain fatty acids.

The fatty acids used are preferably those with 10 to 24, in particular 12 to 22 carbon atoms in an amount of about 0.5 to 15% by weight, in particular 1 to 10% by weight, based on the total composition. Behenic acid and stearic acid are particularly suitable; however, other fatty acids such as myristic acid, palmitic acid or oleic acid or mixtures of natural or synthetic fatty acids such as coconut fatty acid can also be used.

Another preferred component in aftertreatment agents is urea, preferably in an amount of about 1 to 10, in particular about 2.5 to 7.5% by weight of the agent according to the invention.

The hair treatment agent according to the invention can contain as a further component at least one compound selected from the group 1-methoxypropanol(-2), 1-ethoxypropanol(-2), diethylene glycol monomethyl or ethyl ether, dipropylene glycol monomethyl
or ethyl ether, benzyl alcohol, benzyloxyethanol, phenylethyl alcohol, phenoxyethanol and/or cinnamyl alcohol, preferably in an amount of 0.5 to 25,

:=&Ggr;·&Ggr;:&Ggr;:&Ggr; 5 X?l i j &Iacgr;

i ii · A-2/00

in particular 1 to 20, especially 2.5 to 15 wt.%, calculated on the total composition of the agent.

Preferred compounds from this group are ethoxydiglycol and benzyloxyethanol.

In principle, water-soluble ingredients are contained in the water phase and water-insoluble ingredients in the oil or fat phase of the W/O emulsion according to the invention, although borderline cases can of course also occur.

The water-in-oil emulsions according to the invention contain at least one suitable W/O emulsifier, preferably at least one non-ionic surfactant,

These are generally known and are described in detail, for example, in the monograph by K. Schrader, I.e., pp. 387 to 525, to which, in order to avoid repetition, explicit reference is made here.

Usually, emulsifier mixtures are used, e.g. from (poly)glycerol fatty acid esters with fatty alcohol polyglycol ethers.

The use of co-emulsifiers such as higher fatty alcohols is also common and useful.

For details, reference is made to the known state of the art, which also describes in detail the possible use of inorganic and organic hydrocolloids, consistency regulators, stabilizers, etc. (cf. Schrader, I.e., pp. 407 to 411).

The proportion of W/O emulsifiers in the overall composition depends on their structure and HLB value and is about 2.5 to 25, in particular about 5 to 15 wt.%, depending on the type of other components present, in particular the oils, fats and waxes and their possible surface-active properties.
The same applies to the ratio of water phase to oil or fat phase in the W/O emulsion, dqx ':l can be about 10:90 to 90:10, but is preferably about 20:80 to 80:20, in particular about 25:75 to 75:25.
The production of such W/O emulsions is also known in principle; it is usually carried out by melting the fat phase at an elevated temperature and then adding the water phase while stirring, cooling and homogenizing.

: ^A ' ^2/0 °

However, under certain conditions and with certain compositions, cold emulsification is also possible.

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

• *··· ··· ;*1&iacgr;&idigr;&idigr; α-2/00

example 1

A W/O emulsion was prepared by melting the fat and oil phase at 70 ^° C and then adding the water phase while stirring until a homogeneous composition was achieved.

Fat and oil phase:

Pea protein hydrolysate (from Pisum sativum) 0.5 (wt%) Total protein content ~ 90% (less than 0.2% w/w soluble in H ₂ O at 20 ⁰ C) W/O emulsifier (PEG-30 dipolyhydroxystearate) 3.0 Caprylic-ZCapric acid triglyceride 4.0 PCL Liquid 4.0 Paraffin oil 2.0 vaseline 4.0

Water phase:

1,2-Propanediol 2.0 (wt.%)

MgSO ₄ × 7H ₂ O 0.7

Glycerine 4.0

Vinylpyrrolidone/vinyl acetate copolymer 2.0

Water ad 100.0

This W/O emulsion remained stable after storage for six months at 40°C. In the half-side test, the product was massaged into one half of freshly shampooed, towel-dried hair, the other half was treated in the same way with an identical product (Example 1X) which, however, did not contain pea protein hydrolysate.

After 30 minutes, both halves were judged by a hairdresser in a blind test and classified according to a better-equal method.

The result showed a clear preference in favour of the composition according to the invention according to Example 1: ;

Characteristics Example 1 better
■ '.'■■ ■ ■ Same Example 1 X better Distributability of the product 6 2 2 Drying speed
in the hair 4 4 2 Shine of hair 6 4 0 Strengthening the hair 8th 2 0 Volume, handle of hair 8th 2 0 Stickiness of hair 10 0 0 Appearance (fatness) of the
Hair 9 1 0 Looseness of hair 8th 2 0 Overall assessment 9 1 0

Example 2

A W/O emulsion was prepared analogously to the procedure described in Example 1.

Fat and oil phase:

PEG-30 dipolyhdroxystearate PEG-7 hydrogenated castor oil isohexadecane

Caprylic/capric acid triglyceride Isopropyl myristate Pea protein hydrolysate (analogous to example 1)

2.5 (wt.%) 2.5 6.0 4.0 4.0 1.0

Water phase:

1,2-propanediol MgSO ₄ x 7H ₂ O glycerol

2.0 (wt.%) ΔJ :. 4.0

Isobutylene/maleic acid copolymer 5;0

(Aquaflex ^R FX64) / ;

Water ad 100.0

This W/O emulsion had similar good properties as that of Example 1.

Example 3

Analogously to the procedure described in Example 1, a W/O emulsion of the following composition was prepared:

Fat or oil phase:

Potato protein hydrolysate 0.5 (wt.%) (solubility in 100 ml H ₂ O at 20°C:< 0.25 g)

Pea protein hydrolysate 0.5 (solubility in 100 ml H ₂ O at 20°C:< 0.3 g)

PEG-30 dipolyhydroxystearate 2.0

Neo-PCL self-emulsifying W/O 2.0

Triglyceride diisostearate 1.5

Isostearic acid diethanolamide 1.5

2-Octyldodecanol 20.0

Vaseline 12.0

Capryl-ZCapric acid triglyceride 4.0

Isopropyl stearate 3.0

Water phase:

1,2-Propanediol 3.0 (wt.%) MgSO ₄ &khgr;7H ₂ O 0.7 Glycerine 3.0 N-octylacrylamide/acrylic acid 2.5 N-tert. Butylaminoethyl methacrylate terpolymer (Amphomer ^R ) Polyvinylpyrrolidone 1.0 Aminomethylpropanediol q.s. Preservatives q.s. Water ad 100.0

A stable product with excellent hair conditioning properties was obtained.

Claims (4)

1. Hair care product consisting of a water-in-oil emulsion, characterized in that the aqueous phase of the emulsion contains at least one water-soluble polymer and the oil or fat phase of the emulsion contains at least one vegetable protein hydrolysate which is sparingly soluble in water. 2. Agent according to claim 1, containing 0.25 to 10 wt. %, calculated on the total composition, of at least one water-soluble polymer. 3. Agent according to claim 1 or 2, containing 0.1 to 7.5 wt. %, calculated on the total composition, of at least one poorly water-soluble plant protein hydrolysate. 4. Agent according to one of claims 1 to 3, characterized in that the plant protein hydrolysate has a molecular weight between about 10,000 and about 800,000 g/mol.