CA1221914A - Oxidative hair dye composition - Google Patents

Abstract

Abstract of the disclosure An oxidative hair dye composition is provided with a viscosity vs. shear rate curve having a steep slope and having good stay-put characteristics when observed on a sloping substrate. The composition has a viscosity of from about 3,200 cps to about 10,000 cps at low shear rate of 8.5 sec-1, a viscosity of from about 70 cps to about 150 cps at a high shear rate of 1,370 sec-1, and manifests a maximum of 1 inch flow on a sloping substrate.

Description

CP ` ~001 - OXIDATIVE ~IAIR DYE COMPC)SITION
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1. Field of the Invention _ ~ he present invention relates ~o aqueous oxidative hair dye compo~itions with unique rheological properties. The hair dye compositions of the presen~ invention have excellent flow-on and ~ay-put pr~perties.

2. Backqround of the Invention The physical properties of oxidative hair dye compositions of the prior ~rt ~enerally represent a compromise between the flow charac-teristics required at different stages of the dyeing process. ~hen an ~xidative hair dye composition i~ applied to the hair, it should be of a suitably fluid c:haracter ~o that it flows on, and cover~
each entire hair shaft within the mass of hair on the head. On the ~ther hand, if the dye remains too flu~d after application to the -hair, then, the dye will undesirably run and drip off the head. If the latter problem is intended to be avoided by making the dye rather vi~cous, when it will not flvw de~irably on to the hair at the time of application of the dye.

3. Description of the Invention We discovered an oxidative hair dye composition which has favorably ~ariable viscosity characteri~tics, including a low shear rate tBJ5 ~ec 1) viscosity from about 3,200 to about 10,0~0 centipoises (cps) and a high ~hear rate ~1,370 sec 1) visoosity from about 70 to about 150 ~p~ and a tay-put flow path of n~t more than 1 inch. The compositi~n of the present invention compri~es, ba~ed on the weight of the entire composition, of from about 5 to about 10 percent of a fatty acid containing between 18 and 22 carbon atoms in the molecule, sufficient alkalizer to neutralize ~aid ~atty acid ~nd to establi~h in the hair dye composition ~ p~ between 8.5 and ll.S, from about 1.25 percent ~o about S percent of a fatty alcohol having between 12 an~.22 carbon atoms in the m~lecule, '~

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and from about 10 percent to about 15 percent of at least one alkoxylated alkyl phenol having an HLB from about 9 to about 11.5.
All percentages are hy weight unless specified otherwise. All chemical names are used in accordance with the nomenclature employed by the CFTA Cosmetic Ingredient Dictionary, published by The Cosmetic Toiletry and Fragrance Association, Inc. in 1982.
All parameters are at room temperature.
In a preferred emboaiment, the oxydative hair dye composition will comprise from ahout 1.5 to about 6~ of a hair dye oxidant expressed as absolute hydrogen peroxide.
Thus, the present invention provides a hair dye composition, having marked thixotropic properties, i.e. the viscosity as a function of shear rate curve having a rather sharp slope~ This means that when the hair dye composition containing the base composition of the present invention is subjected to high shear, e.g. when it is agitated when applied, and for a relatively short period thereafter, its viscosity is rather low. This results in it being sufficiently fluid to flow well onto the hair upon application.
After it was applied to the hair, the composition will become in-creasingly viscous and will not drip or run off the hair. Compara-tive tests with a large number of commercial hair dye compositions have proven the superiority of the flow characteristics of hair dye compositions prepared in accordance with the present inYention.
The HLB of an emulsifier is determined in accordance with the detailed description contained in the booklet entitled ~he Atlas HLB
System, published by Atlas Chemical Industries, Inc. The letters HhB stand for hydrophile-lipophile balance. This system was introduced by Atlas Chemical Industries in the late 1940's as a sy-stematic scheme for the designation of the emulsifying characteris-tics of materials. Each emulsifier is assigned a numerical value which is referred to as its HLB. The numerical value refers to the balance of the size and strength of the hydrophilic or polar and the lipophilic or non-polar groups in each emulsifier, since all emulsifiers consist of a molecule that combines both hydrophilic and lipophilic groups. An emulsifier that is lipophilic in character is assigned an HLB below 9 and one that is hydrophilic is assigned an HLB above 11. Those between HLB 9 and HLB 11 are considered intermediate in character.
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When a plurality of emulsifiers are mixed, the composite HLB of t mixture is an arithmetic total of the product of the per-centage of a given ingredient and its HLBD For example, in the case of a suitable combination of the alkoxylated alkyl phenols nonoxylnol-9 ~LB 13) r and nonoxylnol-4 (HL~ 8.B), when both are present in identical concentrations the resulting HLB of the mixture i5 10- 9. Other suitable alkoxylated alkyl phenols or blends thereof will ~e readily apparent to those having an average skill in the art ~f hair dye formulations.

Since the oxidizer is an essential ingredient of the composi-tions of the present invention, and since the oxidizer, or developer composition as it is referred to in the hair dyeing art, has to be maintained apart from the composition containing one or more hair dye intermediates (often referred to as the "tint" in the hair dyeing art), and since both the develo~er and tint compositions are aqueous solutions, it is preferred that at least a part of the alkoxylated alkyl phen~l emulsifier be contained in the developer composition~ This will promote the easier blending of the developer compositivn with the tint composition when both are mixed with each other prior to use.

Illustrative of the C18-C22 fatty acids that can be employed with the present invention are stearic acid, behenic acid, arachidic acid, arachidonic acid/ oleic acid, linoleic acid or mixtures o~
acids, such as from natural sources, e.g. tall oil acid. These acids can be saturated or unsaturated.

A variety of C12-C22 fatty a~cohols can be employed in the invention, such as lauryl, oleyli, stearyl, isostearyl, cetyl, ~yristyl, behinyl alcohol and the like. These alcohols can have a caturated, unsaturated, straight chain or branched structure.

The alkalizer can be any material ~onventionally employed in hair care ~ompositions, such as ammoninum hydroxide, monoethyanolamine, and the like, to neutralize the fatty acid and to establish the requi~ite alkaline pH.

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Although the oxidizer is expressed in terms of hydrogen pe~_~ide, other oxidizerfi uitable for use in hair treating compositions, such as other peroxides, e.g. urea peroxide, can also be employed. While it is to be understood that even though reference is made througho~t the specification in the claims to a hair dye composition, the present invention, as disclosed throughout the specification and the claims is al o intended o include mild bleaches which do n~t necessarily contain hair dye intermediates which produce a color. Normally, however, compositions intended primarily for the bleaching of hair also contain bleach boosters, 6uch as powdered percompounds in addition to an oxidizer, such as hydrogen peroxide. It was found, however, that the beneficial variable viscosity characteristic6 of the present invention could not be obtained when such bleach boosters were added to the composition.

The flow properties of the c~mposition of the present invention were compared to a relatively large number of commercially available oxidation hair dyes. The data concerning these comparisons are presented herein, following the examples. All of the commercially available compounds exhibited a certain amount of shear rate dependence in their viscosity, however~ none of them have demonstrated the high degree of ~hear rate dependence as those of the present invention. Therefore, it appears that in formulating the commercial compositions of the prior art a tradeoff ~as necessary either to provide a.high viscosity at low ~hear rates ~to assure good stay-put properties-, or to provide sufficiently low viscssities at high shear rates -to provide good flow-on properties-, but not both. With a minor exception, it appears that the formulato~s of the commercia~ compositions generally chose to provide low viscosities at high ~hear rates, at the expense of obtaining insuffici~ntly high viscosities at-low ~hear rates. ~o ~uch tradeoff i~ necessary in the case of the compositions of ~he present invention,~because the considerably 6harper 6hear rate dependence of the viscosity values permit~ the achievement ~f ideal viscosities at both the high and low ends of the ~hear rate range.

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In another embodlment the present invention provides a package including two containers, the contents of which are intended to be combined with each other before use, each of said containers containing an aqueous composition, wherein one container contains an oxidative hair dye tint composition which comprises from about 5% to about 10%
by weight, based on the weight of the contents of both containers, of a fatty acid containing from about 18 to about 22 carbon atoms in the molecule; sufficient alkalizer to neutralize said fatty acid and to establish a pH from about 8.5 to about 11.5 in the composition after the contents of the two containers are combined; and from about 1.25%
to about 5% of a fatty alcohol having from about 12 to about 22 carbon atoms in the molecule; and the other con-tainer contains an oxidative hair dye developer composition which comprises from about 10 percent to about 15%, based on the weight of the contents of the both containers, of at least one alkoxylated alkyl phenol having an HLB, or a plurality of such phenols having a composite HLB, from about 9 to 11.5; and from about 1.5% to about 6% of a hair dye oxidant, expressed as absolute hydroyen peroxide.
Following the examples there is a listing given of many of the commercial oxidative hair dye products that were used in this -4a-comparison, on the basis of the irlgredient listings on their la. .s. This information was avai.lable only for those commercial hair dyes which are sold in the United States, because no ingredient listing i5 required in other countries. None of the commercial oxidati~e hair dyes for which the ingredients are available, contain the unique com~ination of ingredien~s of the present invention.

Srnce the shear rate-dependent viscosity measurements of compositions in accordance with the present invention and of co~mercial oxidative hair dye compositions indicated that the formulators of the commercial compositions apparently intended primarily to assure g~od low-on properties during application of the dyeing composition to the hair, ~ f~rther series of tests were made. In this series of tests the high viscosity stay-put properties of,compositions in accordance with the present invention and of commercia~ compositions were compared. A dab 4f each oxidative hair dye composition was placed onto the top of an inclined board and after five minutes the distance that each sample traveled, was measured. The data of these comparative stay-put tests are also provided following .the examples. These data show that only one commercial hair dye composition (Polycolor Creme Haircolor 45) had stay-put properties similar to those of the compositions of the present invention. ~he high shear-rate viscosity data for that same commercial composition indicate, . however, a relatively high viscosity value which suggests comparatively unfavorable flow-on properties and, of course, indicates that the tradeoff in the case of this commercial composition was weighted towards providing high viscosity at low shear rates for better stay-put properties. As explained below, the ~tay-put tests further revealed that high viscosity at low shear rates does not necessarily assure good stay-put properties of a dye composition. Therefore, in addition to the requirement that the composition have a,vi6cosity at a low shear rate of 8.5 sec 1 of from about 3,200 to about lO,OOOcps, it is a further requirement that on the stay-put test it ~hould have a travel di~tance of not more than 1 inch.

A number of comparative experiments were carried out for deter-mining the essential ingredi~nt~ which contribute to the favorable rheological properties in accordance with the present invention.
These comparative experiments not only established the essential L$~

i edients which contribute the desirable properties, but also es-tablished that while it might be expected that the low shear viscosity values are ~omewhat in~icative of the stay-put characteristics of the composition, the stay-put flow test on the inclinea substrate is an at least equally if not more important characteristic~ Therefore, a high low shear viscosity does not nec-essaEily result in an acceptable stay-put results on the inclined plate.

A tint base containing the following ingredients, expressed as percent by weight, based on the tint base composition, serYed as the basis of comparison.

lauramide DEA 3.0 ammonium hydroxide 8.7 cetyl alcohvl 2.5 oleic acid 12.0 laureth-23 0~5 water to 100 An equal volume of the developer o Example 3 was employed in these tests. The base had a low shear (8.5 sec 1) Yiscosity o 5324 cps and a high ~hear (1370 sec 1) viscosity of 101 cps, and in the stay-put llow test it did not show any movement.

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"he following table summarizes the comparative results. The first column of the table indicates the difference between the sample and the above-mentioned tint base-composition.

Sample Flow Dist.(in) Shear Rate(sec 1) Viscosity(cps) oleic acid omitted 9 8.5 1521 cetyl alcohol omitted 3.5 8.5 1711 lauramide DEA omitted 1 8.5 3423 laureth-23 omitted 0 8.5 6465 lauramide DEA and laureth-23 omitted 0 8.5 4563 oleyl alcohol instead of cetyl alconol 0 8.5 7225 lauric acid instead of oleic acid 10 8.5 950 lauryl alcohol instead of cetyl alc. 0 8.5 6465 palmitic acid instead of oleic acid 6 8.5 1521 myristic acid instead of oleic acid 9 8.5 950 isostearic alc. instead of cetyl alcohol 1 8.5 3802 ~2~

A further series of similar comparative kests were made to determine the other essential ingredients which are contributed to the hair dye composition through the developer component.
Accordingly, it was found that the oxidizer is an essential ingredient and so is the presence of from about 10~ t~ about 15% ~y weight, based on the hair dye composition, of an alkoxylated and alkyl phenol having an ~LB of from about 9 to about 11.5.

The following illustrative examples demonstrate embodiments of the present invention. All percentages are by weight of the composition of the examples, unless indicated otherwise.
Example 1 The following C,or~ositiQn is a tint component of an oxidative hair dye composition to provide light bro~n dyeings.

ammonium hydroxide 8.7%
cetyl alcohol 1.5 stearyl alcohol 1.0 lauramide DEA3 3.0 oleic acid 12.0 fragrance 0.1 laureth-23 0.5 phenylenediamide 0.27 N,N bis(2-hydroxyethyl~
p-phenylenediamine sulfate 0.11 l-naphthol 0.1 resorcinol 0.85 sodium sulfite 0.1 erythorbic acid 0.2 EDTA 0.05 water to 100 The tint composition contains ammonium hydroxide, 2 fatty alcohols (cetyl and stearyl) and oleic acid which are the critical ingredients of the composition of the present invention.

,,~ ~, ., Exa~ 2~
The following tint composition was prepared to provide a blonde ~hadeO

ammonium hydroxide 9.o%
. cetyl alc~hol 4,5 lauramide DEA3 3.0 oleic acid 13.0 fragrance 0.1 laureth-23 0.5 p-phenylenediamine 0.06 N,N bis~2-hydroxyethyl) p-phenylenediamine sulfate 0.16 l-naphthol 0.03 resorcinol 1.0 sodium sulfite 0~1 eryth~rbic acid 0.2 EDTA 0.05 water to 100 Example 3 .

The fo~lowing developer was prepared for use in conjunction with the tint compositions of Example 1 or Example 2.

n~noxynol-~ ~ooo%
nonoxynol-4 10.0 EDTA . 0.02 hydr~gen per~xide - 50% ' 12~3 water to 100 , The hair dyein7 composition i formed by mixing equal parts by volume of either ~ the tint compositi~ns of Example 1 or Example 2 and the developer composition of Example 3. Mixin~ i~ accomplished either by shaking the mixture in an applicatsr bottle from which it can be directly applied through a spout to the hair, or by blending the two compositions in a mixing bowl and then applying the mixture with an applicator brush; as ~s customary in the hair dyeing art.
The viscosity measurements comparing the c~mmercial oxidative hair dyes with the compositions pr.epared in accordance with the pr-sent invention, were carried Ollt on the Haake Rotovisc~
vi~cometer. The mea~urements are summarized in the following table, wherein the viscosity in cen~ipoises lcPs~ is given for each material at a low ~hear rate of B.5 sec 1 and at 1,370 ~ec 1 high ~hear rate. All compositions employed the respective developer compositions o~ the commercial samples except in the case of the present invention where the devel~per of Example of 3 was employed.
sample shear rate viscos~y Example 1 8.5 4563 Preference 5 8.5 2282 Excellence 6 8. 5 3042 1370 1~ 0 Nice 'n Easy 115 8. ~ 950 Miss Clairol Creme Formula 36 8.5 2472 Clairesse 214 80 5 1711 Miss Clairol Shampoo Formula 36 8.5 1331 Kolestone 1200N 8.5 2472 1370 8~
Majiblond 901 8.5 2472 i 1370 1~5 Example 2 8.5 5894 Haute ~lode A B. 5 3993 Polycolor Creme Haircolor 43 ~. 5 3993 Polycolor Tonungs Wasche 18 8.5 951 1370 ~

The ~tay-put flow test compariF~ons of the compositions of the present invention with the commercial oxidative hair products were carried out by ~potting 0.59 of each hair dye compositi~n, respectively, onto a ~tiff cardboard Which was inclined at an angle Df 60. After five minutes the distance to which each droplet flowed downward was measured. Ihe distances in inches traveled by the Yarious samples are ~hown in the following table~ In the case ~f ~he commercial oxidation dyes the developer of that prod~ct was used. In the case of the compositivns in ~ccordance with the present invention the developer of Example 3 was employed. The num~er~ following 60me commercial ~amples indicate ~hade designations.

Sam~le Flow Lenqth (inches) Example 1 0 Example 2 0 ~ice'n Easy* 1.7 Preferenc~ 9 1/2 B~ 2.7 Excellence 6 2. 8 Haute ~ode A 2.2 Miss Clairol*5hampoo Pormula 36 1~7 Miss Clairol*Creme Formula 36 0~9 Clairesse*206 ~n3 Kolestone 800N 2.6 Majiblond* 1.8 Polycolor Tonung s Wasche 18 3 0 3 Polycolor Creme ~aircolor 45 0 In the case of the last commercial sample which demonstrated a good stay-put ~low characteri~tic the high ~hear viscosity data for this ~ample sh~w that in formulating this product the flow characteristics were apparently compromised tnwards higher viscosity.

From the labels cf the commercial product6 ~old in the United States and used for comparisons herein, the following compositions could be ascertained.

Preference, tint: ammonia, oleic acid, oleyl alcohol/ cocamide DEA, polyglyceryl-4-oleyl ether, polyglyceryl-2-oleyl etherO
Developer: ceteth-2, oleamide DEA.

Nice'n Easy, tint: ammonia, ~leic acid, ~ctoxynol-l, nonoxynol-4, cocamide ~EA. Developer~ nonoxynol-9, nonoxynol-4, cetyl alcohol, s~earyl alcohol.
' * Trade mark ~ s Clairol Sh~ F ~-~la, tint: ammmonia, tall oil fatty acid, octoxynol 1, nonoxnol~4, linoleamide DEA. Developer:
nonoxynol-9, nonoxynol~4, cetyl alcohol, stearyl alcohol~

Mîss Clairol Creme Formula, tint: ammmonia, oleic acid nonoxynol-4, octoxynol ~, sodium lauryl ~ulfate. ~eveloper:
water.

Excellence~ tint: ammonia, triethanolamine, ammonium laureth sulfate, pareth-15-9, pareth-15-3. Developer~ Ceteth-2, oleamide DEA.

Clairesse, tint: Monoethanolamine, octoxynol-l, nonoxnol-9, linoleamide-DEA. Developero nonoxynol~9, nonoxynol-9, cetyl alcohol, stearyl alcohol.

Claims (10)

We Claim:

1. An oxidative hair dye composition which spreads easily when applied to the hair and stays in place once applied to the hair said composition having a viscosity at room temperature of from about 3,200 to about 10,000 centipoises at a shear rate of 8.5 sec-1, a viscosity of from about 70 to about 150 centipoises at a shear rate of 1.370 sec-1, and a maximum stay-put flow distance of one inch.

2. In an oxidative hair dye composition having an alkaline pH and which contains an oxidizer and water, the improvement which comprises from about 5% to about 104 by weight of a fatty acid containing from about 18 to about 22 carbon atoms in the molecule, sufficient alkalizer to neutralize said fatty acid and to establish a pH from about 8.5 to about 11.5, from about 1.25% to about 5% of a fatty alcohol having from about 12 to about 22 carbon atoms in the molecule, and from about 10% to about 15% of at least one alkoxylated alkyl phenol having an HLR, or a plurality of such phenols having a composite HLB, from about 9 to about 11.5.

3. The oxidative hair dye composition of claim 2 wherein the composition comprises from about 1.5% to about 6% of a hair dye oxidant, expressed as absolute hydrogen peroxide.

4. The oxidative hair dye composition of claim 3 wherein the fatty acid is saturated or unsaturated and the fatty alcohol is a saturated or unsaturated and has a straight-chain or branched structure and said composition contains at least one oxidative hair dye intermediate.

5. The oxidative hair dye composition of claim 4, wherein the fatty acid is at least one of stearic, behenic, arachidic, arachidonic, oleic, linoleic and tall oil acid.

6. The oxidative hair dye composition of claim 4, wherein the fatty alcohol is at least one of lauryl, oleyl, stearyl, isostearyl, cetyl, myristyl and behinyl alcohol.

7. The oxidative hair dye composition of claim 4, wherein the alkoxylated alkyl phenol is an ethoxylated alkyl phenol.

8. The oxidative hair dye composition of claim 2 or 3, wherein said fatty acid is at least one of stearic, behenic, arachidic, arachidonic, oleic, linoleic and tall oil acid; said fatty alcohol is at least one of lauryl, oleyl, stearyl, isostearyl, cetyl, myristyl and behinyl alcohol; the alkoxylated aklyl phenol is an ethoxylated nonylphenol; and the neutralization of the fatty acid and the adjustment of the pH are carried out with ammonium hydroxide.

9. A package including two containers, the contents of which are intended to be combined with each other before use each of aid containers containing an aqueous composition, wherein:
a) one container contains an oxidative hair dye tint composition which comprises (i) from about 5% to about 10% by weight, based on the weight of the contents of both containers, of a fatty acid containing from about 18 to about 22 carbon atoms in the molecule;
(ii) sufficient alkalizer to neutralize said fatty acid and to establish a pH from about 8.5 to about 11.5 in the composition after the contents of the two containers are combined; and (iii) from about 1.25% to about 5% of a fatty alcohol having from about 12 to about 22 carbon atoms in the molecule; and (b) the other container contains an oxidative hair dye developer composition which comprises (i) from about 10 percent to about 15%, based on the weight of the contents of the both containers, of at least one alkoxylated alkyl phenol having an HLB, or a plurality of such phenols having a composite HLB, from about 9 to 11.5; and (ii) from about 1.5% to about 6% of a hair dye oxidant, expressed as absolute hydrogen peroxide.

10. The oxidative hair dye composition of claim 2 wherein the fatty acid is saturated or unsaturated and the fatty alcohol is a saturated or unsaturated and has a straight-chain or branched structure and said composition contains at least one oxidative hair dye intermediate.