DE20018140U1 - Hydrogen peroxide preparations - Google Patents

Description

Description Hydrogen peroxide preparations

The invention relates to oxidizing agent preparations containing hydrogen peroxide and certain associative thickeners, which are particularly suitable as oxidizing agent preparations for use in the bleaching and oxidative dyeing of keratin fibers, in particular human hair, or as fixing agents in the permanent shaping of hair.

Oxidizing agent preparations are usually in the form of aqueous, preferably thickened solutions or emulsions.

Both oxidation dyes and bleaches usually consist of two components, (i) the dye carrier or bleach containing the dyes and (ii) the oxidation agent preparation, which are mixed together shortly before use and then applied to the hair to be dyed/bleached.

Oxidizing agent preparations containing hydrogen peroxide should be able to be mixed quickly and homogeneously with other components, for example the dye carrier mass, and should adhere very well to the fiber. Liquid oxidizing agent preparations are difficult to process and often do not produce a homogeneous, ready-to-use dye/bleach preparation. Emulsion-like oxidizing agent preparations are much easier to process, but they also only partially solve the problem of the insufficient miscibility of the oxidizing agent preparation with the other components.

In addition, the ready-to-use dye/bleach preparations often do not achieve the desired coverage or adhesion to the hair or cannot be applied with sufficient precision.

A large number of proposals have already been made to solve the above-mentioned problems. For example, DE-OS 37 32 147 proposes an emulsion-like hydrogen peroxide preparation which contains 1 to 5 percent by weight of a C16 to C20 fatty alcohol and a thickening polymer or copolymer containing carboxyl groups. Although the above-mentioned problems can be partially solved by using such an emulsion-like hydrogen peroxide preparation, such preparations only inadequately meet the requirements placed on oxidizing agent preparations, in particular with regard to miscibility and color intensity.

There was therefore still a need for oxidizing agent preparations which meet the above-mentioned requirements to a particularly high degree.

It has now been found that certain hydrogen peroxide preparations containing associative thickeners meet the above requirements to a particularly high degree. The agent according to the invention has in particular an ideal miscibility of the oxidizing agent preparation with the other components and also enables coloring or bleaching with an extraordinarily high covering power and adhesion to the hair.

The invention therefore relates to oxidizing agent preparations containing hydrogen peroxide or its addition compounds, which are characterized in that they contain at least one non-ionic, amphiphilic associative thickener in a suitable cosmetic carrier.

The nonionic, amphiphilic associative thickener is preferably contained in the composition according to the invention in an amount of about 0.01 to 20 percent by weight; in particular from about 0.1 to 10 percent by weight.

A polymer containing both hydrophilic and hydrophobic groups is used as a nonionic, amphiphilic associative thickener. Associative thickeners are water-soluble polymers and have surfactant-like hydrophobic components that are able to associate, i.e. interact, with themselves and with other hydrophobic substances in a hydrophilic, particularly aqueous, medium. The resulting associative network thickens or gels the medium. Associative thickeners are typically produced by polymerizing polyethylene oxide prepolymers and at least doubly functional, polycondensable substances such as isocyanates, with monohydroxy compounds or dihydroxy compounds with large aryl groups, alkyl groups or aryl/alkyl groups being incorporated to provide the hydrophobic modification. Preferred associative thickeners are therefore hydrophobically modified polyalkylene glycols. The hydrophilic component is formed by polyoxyalkylene units, preferably polyoxyethylene units but also polyoxypropylene units or their mixture. The hydrophobic component is

• φ φφφ
ϕ ϕ ϕ ϕ
Φ Φ ΦΦ
Φ Φ Φ Φ
Φ Φ Φ Φ
φ· · Φ
Φ Φ
Φ Φ &phgr;
O Φ; Φ Ml
ϕ ϕ &bgr;
Φ ϕ φ
ϕI Φ
&phgr; Φ
Φ Φ Φ
Φ Φ Φ
Φ Φ Φ; Φ; Φ; Φ; Φ; I ϕ φ
φ Φ Φ Φ Φ Φ Φ
Φ; Φ; Φ; Φ; Φ; ϕ φ
Φ Φ &phgr;
ΦΦ Φ Φ Φ
ΦΦΦΦΦΦ Φ Φ
Φ ΦΦΦ •

preferably formed from hydrocarbon groups, for example long-chain alkyl groups, alkylaryl groups or arylalkyl groups. Particularly preferred associative thickeners are hydrophobically modified aminoplast-polyether copolymers. For their structure and preparation, reference is made to WO 96/40815. WO 96/40815 describes water-dispersible or water-soluble copolymers which are the reaction products of an acid-catalyzed polycondensation of at least doubly functional aminoplast monomers and at least doubly functional alkylene polyethers and also monofunctional compounds with hydrophobic groups. Suitable aminoplasts can be found in Figure 1 of WO 96/40815. The glycoluril derivatives of the formula X of WO 96/40815 are particularly preferred. Suitable alkylene polyethers can be found in Figure 2 of WO 96/40815. Preferred alkylene polyethers are polyethylene oxide diols. These can have a degree of ethoxylation of 20 to 500, preferably 50 to 350, particularly preferably 100 to 250. Suitable simple functional compounds with hydrophobic groups are those of formula XIV of WO 96/40815.

Associative thickeners suitable according to the invention are preferably selected from polymers of the general formula (I)

(OR) _n

C)

where Amp is an aminoplast monomer or the residue of an aminoplast oligomer or aminoplast polymer, AO is a

alkylene oxide group, R represents hydrogen, a C1-C4 alkyl group or a C1-C4 acyl group and &khgr; and y are numbers greater than 1.

Particularly preferred are the reaction products of the acid-catalyzed polycondensation of (a) glycolurils of the general formula (II),

MeO-'" ^0Me

^X - R (II)

where R is H or preferably OMe, with (b) polyethylene oxide diols having a degree of ethoxylation of from 20 to 500, preferably from 50 to 350, particularly preferably from 100 to 250, and (c) an optionally ethoxylated hydrophobic alcohol, alkylphenol, thiol, carboxamide, carbamate or a hydrophobic carboxylic acid, as described on pages 1 to 19 of WO 96/40815. A particularly preferred glycoluril is 1,3,4,6-tetramethoxymethylglycoluril (TMMG).

Particularly suitable associative thickeners are those with the INCI names Polyether-1, PEG-180/Octoxynol-40/TMMG Copolymer and PEG-180/Laureth-50/TMMG Copolymer and are sold, for example, by Süd-Chemie AG, Munich/Germany under the trade names Pure-Thix® HH, L, M, TX-1442, TX-1450, TX-1451, TX-1452 and TX-1499.

The oxidizing agent preparation according to the invention contains hydrogen peroxide or its addition compounds as oxidizing agent, for example the addition compounds of hydrogen peroxide to

Urea, melamine or sodium borate, wherein the amount of hydrogen peroxide in the composition according to the invention is preferably about 0.1 to 30 percent by weight, in particular about 0.5 to 18 percent by weight, in particular about 1.5 to 9.

For stabilization, the preparation according to the invention can contain anionic surfactants. Suitable anionic surfactants are in particular those which have a linear alkyl group or alkenyl group with 12 to 18 C atoms and an anionic group bonded to it, for example a -SOV"* or -O-(C ₂ H4O) _z -SO3 ⁽ " ⁾ group, in which ζ can be equal to a number from 0 to 20. Examples of such preferred anionic surfactants are alkyl sulfates, alkanesulfonates, a-olefinsulfonates, alkyl polyglycol ether sulfates and alkyl polyglycol ether sulfonates. Other suitable anionic surfactants are sulfosuccinic acid monoester salts, alkyl polyglucose ether carboxylates, oleic acid sulfonates and other high-foaming, anionic sulfate or sulfonate surfactants. The anionic surfactants are preferably in the form of their alkali, magnesium, ammonium, or mono-, di- or trialkanolammonium salts with 2 to 4 C atoms in the alkanol group. They are preferably contained in the preparation according to the invention in an amount of about 0.1 to 10 percent by weight.

The hydrogen peroxide preparation according to the invention can also contain an emulsified or dispersed fat phase. Fat components that can be added to the preparation according to the invention include, for example, paraffins, Vaseline, natural or synthetic waxes, hard fats, fatty acid monoglycerides and fatty acid diglycerides and, in particular, linear, saturated fatty alcohols, preferably cetyl alcohol, stearyl alcohol and mixtures thereof, in an amount of about 0.5 to 5 percent by weight. These fat components can either

already mixed in in dispersed form or dispersed in the preparation with the help of the anionic and non-ionic surfactant. In addition to the components mentioned, the hydrogen peroxide preparations according to the invention can contain further auxiliaries. Such auxiliaries are, for example, stabilizers for the hydrogen peroxide, such as dipicolinic acid, quinolinic acid, polyphosphates or acylation products of phosphorous acid, for example 1-hydroxyethane-1,1-diphosphonic acid; buffer substances for setting a pH value of 3 to 5, in particular acidic sodium pyrophosphate (Na ₂ HaPaOz); water-soluble protein derivatives, water-soluble cationic polymers or other hair cosmetically active components and optionally fragrances. The auxiliaries are used in the amounts usual for such agents, for example the hydrogen peroxide stabilizers in an amount of about 0.05 to 1.5 percent by weight.

The agent according to the invention can also contain the additional ingredients customary for such agents, for example perfume oils in an amount of preferably about 0.01 to 5 percent by weight; wetting agents or emulsifiers from the classes of anionic, cationic, amphoteric or non-ionic surface-active substances in an amount of preferably about 0.01 to 10 percent by weight; humectants; preservatives, bactericidal and fungicidal active ingredients in an amount of about 0.01 to 1.0 percent by weight; buffer substances, such as sodium citrate or sodium phosphate, in an amount of about 0.1 to 1.0 percent by weight; care substances, such as plant and herbal extracts, protein hydrolysates and silk hydrolysates or lanolin derivatives, in an amount of about 0.1 to 5 percent by weight; light stabilizers, antioxidants, radical scavengers,

Fatty alcohols, silicone compounds, gloss enhancers, vitamins and moisturising agents in an amount of approximately 0.01 to 10 percent by weight.

The agent according to the invention is preferably formulated in the form of an aqueous preparation. However, aqueous-alcoholic preparations which contain in particular the lower alcohols with 1 to 4 carbon atoms usually used for cosmetic purposes - such as ethanol and isopropanol - can also be used if necessary.

The agent according to the invention preferably has a pH value of about 1.0 to 5.5, with a pH value of 2 to less than or equal to 5 and in particular of 2.5 to 4.5 being particularly preferred. To set the desired acidic pH value, organic or inorganic acids, such as formic acid, tartaric acid, malic acid, maleic acid, fumaric acid, glyoxylic acid, pyrrolidonecarboxylic acid, citric acid, lactic acid, sulfuric acid, acetic acid, hydrochloric acid or phosphoric acid, can be added to the agent according to the invention.

A hair dye or bleach produced with the composition according to the invention meets the requirements placed on such agents in the best possible way in terms of mixability and opacity/decolorizing effect. Furthermore, the ready-to-use agent is much easier to apply due to the improved flow behavior during use and has excellent adhesion to the fiber. The agent according to the invention also enables easy and quick homogeneous mixing with the dye carrier mass or the bleach without the negative accompanying properties that occur with conventional preparations containing thickeners.

For use in oxidative hair coloring or bleaching of hair, the dye carrier mass containing the dyes or the bleaching agent (preferably containing persalts) is mixed with the oxidizing agent preparation according to the invention immediately before use and a sufficient amount for hair coloring, generally about 60 to 200 grams depending on the hair thickness, of the ready-to-use preparation is applied to the hair.

Particularly preferred is the use of a dye carrier mass or a bleaching agent which is also thickened with a non-ionic, amphiphilic associative thickener.

The dye carrier mass or the bleaching agent can be in the form of a solution, a gel, a cream or a powder and can contain the auxiliary substances and additives customary in such agents, which are known to the person skilled in the art from the prior art, for example K. Schrader "Grundlagen und Rezepturen der Kosmetika", 2nd edition (1989), pages 782-823.

The mixing ratio of hair dye/bleach to oxidizing agent depends on the concentration of the oxidizing agent and is generally about 5:1 to 1:3, preferably about 1:1 to 1:2, the content of oxidizing agent in the ready-to-use preparation being about 0.5 to 15 percent by weight, in particular about 1.5 to 9 percent by weight.

The mixture is left to act on the hair at 15 to 50 degrees Celsius for about 10 to 60 minutes, preferably 20 to 30 minutes, then rinsed

• · ♦ ·

Then rinse the hair with water and dry it. If necessary, wash with a shampoo after this rinse and possibly rinse with a weak organic acid, such as tartaric acid. Then dry the hair.

The following examples are intended to illustrate the subject matter of the invention in more detail without limiting it thereto.

Examples Example 1: Gel-like oxidizing agent 10.0 g hydrogen peroxide, 35% aqueous solution 0.2 g phosphoric acid, 85% aqueous solution 2.1 g polyether-1, 20% aqueous solution (Pure Thix® HH) ad 100 g water

Example 2: Fixative for use in permanent hair shaping

15.0 g hydrogen peroxide, 35% aqueous solution 7.0 g PEG-180/Laureth-50/TMMG copolymer, 20% aqueous

Solution (Pure Thix® M)
2.8 g PEG-1 80/Octoxynol-40/TMMG copolymer, 20% aqueous solution (Pure Thix® L)

0.2 g glyoxylic acid, 1 % aqueous solution ad 100 g water

Example 3: Peroxide liquid gel

20.0 g hydrogen peroxide, 35% aqueous solution 7.0 g PEG-180/Laureth-50/TMMG copolymer, 20% aqueous solution (Pure Thix® M )

2.1 g Polyether-1, 20% aqueous solution (Pure Thix® HH) 2.0 g Abil® S 201 (30% solution in isopropanol/water, dimethicone/sodium PG-propyldimethicone thiosulfate copolymer)

0.2 g phosphoric acid, 85% aqueous solution ad 100 g water

Example 4: Creamy oxidizing agent

25.0 g hydrogen peroxide, 35% aqueous solution

7.0 g PEG-180/Laureth-50/TMMG copolymer, 20 % aqueous

Solution (Pure Thix® M)

2.1 g Polyether-1, 20 % aqueous solution (Pure Thix® HH ) 1.5 g Cetyl/Stearyl alcohol

1.0 g sodium cetylstearyl sulfate (Lanette® E) 2.0 g dimethicone/sodium PG-propyldimethicone thiosulfate copolymer, 30% in isopropanol/water (Abil® S 201) 0.2 g phosphoric acid, 85% aqueous solution ad 100 g water

Example 5: Oxidation hair dye

g of a dye carrier mass of the following composition

1.5 g 5-amino-2-methylphenol

1.0 g 4,5-diamino-1-(2'-hydroxyethyl)-1 H-pyrazole sulfate

0.6 g 2,5-diamino-toluene sulfate

0.5 g 2-chloro-6-ethylamino-4-nitrophenol

0.4 g sodium hydroxide, solid

0.6 g ascorbic acid

7.0 g isopropanol

15.0 g oleic acid

12

10.0 g ammonia, 25% aqueous solution

ad 100.0 g water

are mixed with 60 g of an oxidizing agent as per Example 4 immediately before use and applied to blond hair. After a contact time of 30 minutes at room temperature, the hair is rinsed with water and then dried. A reddish-brown hair color is obtained.

Example 6: Oxidation hair dye

g of a dye carrier mass of the following composition

0.33 g 2,5-diamino-toluene sulfate

0.33 g 2,5-diamino-phenylethanol sulfate

0.22 g N,N-bis-(ß-hydroxyethyl)-p-phenylenediamine sulfate

0.33 g 4-amino-3-methyl-phenol

0.22 g 2-aminomethyl-p-aminophenol * HCI

0.22 g 4,5-diamino-1-hydroxyethyl pyrazole sulfate

0.22 g 4,5-diamino-1-(p-methylbenzyl)-pyrazole sulfate

0.11g 1-naphthol

0.11 g 3,4-diaminobenzoic acid

0.11 g 1-(ß-Hydroxyethylamino)-3,4-methylenedioxybenzene * HCl

0.11 g 2,4-diamino-1-(ß-hydroxyethoxy)benzene sulfate

0.11 g 5-amino-6-chloro-2-methyl-phenol

0.11 g 1,3-bis-2,4-(diaminophenoxy)propane * 2HCI

0.11 g 3-aminophenol

0.11 g 4-chloro-resorcinol

0.11g 5-amino-2-methylphenol

0.11 g 2-amino-4-(ß-hydroxyethylamino)anisole sulfate

0.11g 2,4-diamino-1-fluoro-5-methyl-benzene sulfate (1:1)

0.11g 3,5-diamino-2,6-dimethoxy-pyridine * 2HCl

0.11 g resorcinol

0.11 g 2-methyl-resorcinol

0.11 g m-dimethylaminophenylurea

0.02 g 2-amino-5-methyl-phenol

0.02 g 2-amino-6-chloro-4-nitrophenol

0.02 g 4-(ß-hydroxyethylamino)-3-nitrophenol

0.02 g 4-[-3-Hydroxypropylamino]-3-nitrophenol

0.02 g N1-(2-Hydroxyethyl)-2-nitro-p-phenylenediamine (HC Red 3)

0.02 g 4-amino-3-nitrophenol

0.02 g 2-amino-4,6-dinitrophenol, 65% aqueous solution

0.02 g 2-hydroxyethyl picramic acid

0.02 g i-N-Hydroxyethylamino^-methyl^-nitrobenzene

0.02 g 6-ethylamino-2-chloro-4-nitro-phenol

0.02 g 2,6-diamino-3-((pyridin-3-yl)azo)pyridine

0.02 g 4-nitrophenyl aminoethyl urea

11.50 g ammonia, 25% aqueous solution

11.11 g isopropanol

0.38 g NaOH, 20% aqueous solution

0.33 g ethylenediaminoteraacetate

0.33 _{g Na2SO3}

ad 100.00 g water, fully demineralized

are mixed with 60 g of an oxidizing agent as per Example 4 immediately before use and applied to blond hair. After a contact time of 30 minutes at room temperature, the hair is rinsed with water and then dried. A reddish-brown-black hair color is obtained.

14

Example 7: Hair bleach

33 g of a cream-like bleaching agent with the following composition 25.0 g potassium persulfate 18.0 g ammonium persulfate 23.0 g sodium metasilicate 2.0 g sodium alginate 2.0 g xanthan gum 0.5 g acrylic acid polymer (CTFA carbomer) 26.5 g isopropyl palmitate 2.5 g beeswax 0.5 g ethylenediaminotetraacetic acid

are mixed with 50 g of an oxidizing agent according to Example 3 in a bowl using a brush until homogeneous. The ready-to-use bleaching agent thus obtained is applied evenly to the hair to be lightened and rinsed off with water after a contact time of 40 minutes at room temperature. The hair is then dried. The degree of lightening is approximately 4 levels.

All percentages mentioned in this application are by weight unless otherwise stated.

· · ··· *· ·
· · ·· *
· · · ··
· • •
• •
• •
• · ·
· ·· ·
·
« ·
· · ···
•
*
···· ·
·
· · ·
· ·
·· · ·
·
»· · · •
•
•
ft·· ·
···♦
•
• •
•
•
• •
•
• » · ·
· ·

Claims (7)

1. An oxidizing agent preparation containing hydrogen peroxide or its addition compounds, characterized in that it contains at least one non-ionic, amphiphilic associative thickener in a suitable cosmetic carrier. 2. Oxidizing agent preparation according to claim 1, characterized in that the nonionic, amphiphilic associative thickener is selected from hydrophobically modified polyalkylene glycols. 3. Oxidizing agent preparation according to claim 1, characterized in that the nonionic, amphiphilic associative thickener is selected from hydrophobically modified aminoplast-polyether copolymers. 4. Oxidizing agent preparation according to claim 1, characterized in that the nonionic, amphiphilic associative thickener is selected from polymers of the general formula (I)


where Amp represents an aminoplast monomer or the residue of an aminoplast oligomer or aminoplast polymer, AO represents an alkylene oxide group, R represents hydrogen, a C1-C4 alkyl group or a C1-C4 acyl group and x and y are numbers greater than 1. 5. Oxidizing agent preparation according to claim 1, characterized in that the nonionic, amphiphilic associative thickener is selected from reaction products of the acid-catalyzed polycondensation of (a) glycolurils of the general formula (II),


where R is H or preferably OMe, with (b) polyethylene oxide diols having a degree of ethoxylation of 20 to 500, and (c) an optionally ethoxylated hydrophobic alcohol, alkylphenol, thiol, carboxamide, carbamate or a hydrophobic carboxylic acid. A particularly preferred. 6. Oxidizing agent preparation according to claim 5, characterized in that the glycoluril of formula (II) is 1,3,4,6-tetramethoxymethylglycoluril. 7. Oxidizing agent preparation according to one of claims 1 to 6, characterized in that the nonionic, amphiphilic associative thickener is selected from polyether 1 , PEG-180/Octoxynol-40/TMMG copolymer and PEG-180/Laureth-50/TMMG copolymer.