Hair treatment compositions having amine derivatives

Abstract

The use of certain alkanolamines is disclosed for use as a partial or total replacement for ammonium hydroxide in hair treatment compositions. When used as hair colorant alkalizing agents, these derivatives show reduced hair fiber damage, effective color lifting, and significant improvements in cytotoxicity and malodor compared to known replacements for ammonium hydroxide.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention is in the field of hair treatment applications. In particular, the present invention relates to an alternative to ammonium hydroxide for softening and swelling the hair cuticle and allowing penetration of agents and hair-benefit actives into the cortex. [Background technology]

[0002] background Hair structure Human hair fibers are generally understood to have an outermost layer called the cuticle. The cuticle contains approximately 6 to 12 layers of overlapping, flattened keratinocytes arranged in a "scale" configuration along the long axis of the hair fiber. The overlapping cell arrangement allows these cells to slide past each other, giving the hair fiber a high degree of flexibility without breakage. The cuticle layer also regulates the amount of water within the hair shaft. The outermost surface of the cuticle is coated with lipid substances that make the hair surface hydrophobic. The scale arrangement and lipid coating of the cuticle also provide barrier properties to the hair fiber. The second layer of the hair fiber below the cuticle is the cortex, where the natural pigment called melanin is found. Due to the translucent nature of the cuticle, melanin in the cortex is usually visible. Cortex cells form a matrix that supports the keratin protein structure. In the cortex, protein fibers composed of long keratin chains are the main component of hair. These keratin chains are rich in the sulfur-containing amino acid cysteine, which forms permanent, thermally stable cross-links in the form of disulfide bridges between keratin chains. Human hair is approximately 14-20% cysteine. Extensive cysteine ​​disulfide bonds give hair about one-third of its strength and generally make it insoluble except in specific dissociating or reducing agents.

[0003] Cuticle softening The present invention relates to softening and swelling of hair cuticles for any purpose, including, but not limited to, relaxing, straightening, perming, strengthening, and coloring hair. Ammonia (solution) is considered the "gold standard" for various types of hair treatments requiring cuticle swelling and loosening. Ammonium hydroxide, an alkalizing agent, raises the pH of hair, swelling and loosening the hair cuticle, allowing active substances and / or reagents to penetrate the hair. However, the use of ammonia has many drawbacks. For example, ammonia gas easily escapes into the surrounding environment upon use, produces a strong, unpleasant odor, and is irritating to the skin, eyes, nose, and throat. These adverse effects can be experienced by those receiving hair treatments as well as those providing the treatments. Ammonia is also known to damage hair by cleaving peptide bonds. For this reason, research into alternative cuticle penetration methods has been ongoing for decades, with mixed results. For example, aminomethylpropanol (AMP) and monoethanolamine (MEA) have been used as substitutes for ammonium hydroxide due to their low odor. Both molecules are known to be used as pH buffers in cosmetic formulations. In terms of their effect on hair, the amine functional group NH2 reacts similarly to ammonia (NH3) in ammonium hydroxide solution, while the ammonia odor is significantly reduced. Nevertheless, AMP and MEA are associated with a substantial increase in hair fiber damage, which remains a major concern in the art. In fact, to date, no treatment has been found that is as effective as ammonium hydroxide in opening the cuticle, while also avoiding or significantly reducing the adverse effects of malodor and excessive hair damage.

[0004] Hair color treatment Although the principles of the present invention may relate to various types of hair treatments, the invention will be described herein with reference to hair coloring treatments.

[0005] Coloring human hair is an extremely popular cosmetic treatment. Currently, there are four basic types of hair color treatments, classified according to color retention. Temporary and semi-permanent treatments are non-oxidative treatments that use colored dyes deposited on the surface of the hair cuticle. Temporary hair dyes are used to color hair for short periods of time (e.g., one day). This type of hair color can be achieved with basic dyes, acid dyes, disperse dyes, pigments, or metallized dyes. Due to their molecular size, temporary dyes cannot penetrate hair and have little affinity for hair, so they typically wash out after one wash. In contrast, semi-permanent dye molecules are relatively small and may exhibit some affinity for hair. This relatively small size allows the dye to penetrate into the cuticle, even allowing some of the dye to reach the cortex. Nevertheless, alkalizing agents may be used in semi-permanent treatments to promote penetration through the cuticle. Therefore, the present invention may find application in semi-permanent hair coloring. As a result of penetrating the cuticle, semi-permanent dyes require approximately 6 to 12 shampoos to rinse out. Temporary and semi-permanent hair coloring products are available as lotions, gels, shampoos, liquid solutions, emulsions, and mousses.

[0006] Permanent hair color treatments provide color that does not wash out with shampoo and effectively lasts until the treated hair grows out. The "dye" in commercial coloring products is actually a colorless dye precursor that is small enough to migrate under the swollen cuticle and diffuse into the cortex. Inside the hair cortex, the precursor undergoes a series of oxidation-reduction reactions to develop the final color. In the field of oxidation hair coloring, we generally refer to two classes of dye precursor molecules: oxidation bases (also known as primary intermediates) and reaction modifiers (also known as couplers or secondary intermediates). By design, the redox potential of primary intermediates is more favorable for oxidation than secondary intermediates, so primary intermediates are oxidized first. The relatively weak oxidation potential means that secondary intermediates, while capable of producing only slight coloring on their own, can be used to contribute highlights. The primary intermediates oxidize to highly reactive species, which then react with electron-rich secondary intermediates to form colorless transient intermediates called leuco dyes. The leuco dyes are rapidly oxidized to the final color conjugated dyes. Due to their size, the conjugated dye molecules resist being rinsed from the cortex.

[0007] Generally, primary and secondary intermediates belong to three aromatic groups: aromatic diamines, aminophenols, and phenols. Primary intermediates are aromatic diamines and aminophenols in which the substituted amino or hydroxy group is located para or ortho relative to the amino group. This configuration confers the property of easy oxidation. Primary intermediates can form quinone, semi-quinone, and imine-quinone structures. Examples of compounds that have found use as primary intermediates include p-phenylenediamine (PPD), 2-methyl-p-phenylenediamine (PTD), p-aminophenol (PAP), 1,4-dihydroxybenzene, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 4,5-diamino-1-(2-hydroxyethyl)pyrazole, 2,4,5,6-tetraaminopyrimidine, o-aminophenol, catechol, and 1,2-benzediamine, among others. Common modifiers are aromatic m-diamines, m-aminophenols, and m-polyphenols. Substituents at the meta-position make these molecules less susceptible to oxidation. Examples include: m-phenylenediamine, 2,4-resorcinol-diaminoanisole, m-chlororesorcinol, m-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, 4-amino-2-hydroxytoluene, and 1,3-benzenediamine.

[0008] Two other essential components of an oxidation hair dye system are the alkalizing agent and the oxidizing agent. Both serve multiple functions. For example, as mentioned above, the dye precursor must be able to penetrate the hair cortex. To facilitate this process, an alkalizing agent (usually ammonium hydroxide) is used to soften and swell the cuticle. In addition, the alkalizing agent also raises the pH of the cortex environment (to approximately pH 9-11), which increases the reactivity of the oxidizing agent. The oxidizing agent (also known as a developer, usually hydrogen peroxide, H2O2) oxidizes the primary intermediate, initiating a cascade of oxidation reactions that converts the colorless precursor dye into the final color complex. However, at the same time, the alkalizing agent converts some of the H2O2 into OOH. - Convert to OOH - is a highly reactive bleaching reagent that neutralizes natural hair melanin or any previously applied oxidized hair color, thus allowing newly applied color to show through without distortion.

[0009] Demi-permanent hair coloring is another treatment to which the present invention can be applied. Demi-permanent hair color, which lasts for approximately 20 to 24 shampoos, occupies a middle ground between semi-permanent and permanent hair color. Demi-permanent hair color treatments utilize a mix of semi-permanent dyes and dye precursors specific to permanent color treatments. The dyes are mixed with an alkalizing agent (e.g., monoethanolamine MEA or aminomethylpropanol AMP), which is less effective at swelling the cuticle than ammonia. The colorless dye precursors penetrate the outer cuticle and, in part, are able to enter the cortex, where the precursor molecules bond to create larger color molecules that resist washing away. Hydrogen peroxide is used, similar to permanent dyes, but at a lower concentration. As a result, existing hair color is not appreciably lifted. Therefore, this type of dye is effective for adding a relatively intense color to hair. Summary of the Invention

[0010] overview The present invention relates to compositions and methods for softening and swelling hair cuticles. The compositions contain specific amine derivatives characterized by electron donor / acceptor groups, which make the compositions useful as keratin-compatible alkalizing agents for softening and swelling hair cuticles. [Brief explanation of the drawings]

[0011] [Figure 1] The only figure shows denaturation temperature data for alkalizing agent compositions containing a combination of 2-dimethyl-amino-2-methyl-1-propanol (DMAMP) and NH3. DETAILED DESCRIPTION OF THE INVENTION

[0012] Detailed Description Unless expressly indicated otherwise, all concentrations of materials and reaction conditions should be understood as being modified by the word "about."

[0013] Unless otherwise specified, all concentrations are given as weight percent of the final composition.

[0014] Terms such as "comprising" mean that the list of elements may not be limited to the elements expressly listed.

[0015] The specific examples shown in this specification are for illustrative purposes only, and the present invention is not limited to these mentioned examples.

[0016] Alkalizing agents Certain C3-C6 alkanolamines, optionally characterized by electron donor / acceptor groups, alone or in combination, may prove useful as alkalizing agents in oxidative and non-oxidative hair coloring applications. Alkanolamines are composed of an alkane backbone with amino and hydroxyl functional groups. These relatively large organic molecules are less volatile than ammonia. However, like ammonia, alkanolamines can generally create a strongly basic environment that can damage hair and skin cells. The amine group is generally believed to be responsible for the damage to hair. In fact, depending on the concentration required to replicate the benefits of ammonia in hair treatment applications, some alkanolamines may produce more odor and damage than ammonia, or may produce less odor and damage. Eleven alkalizing agents of particular interest are listed in Table 1 (excluding ammonium hydroxide, MEA, and AMP, which are included for comparison purposes only).

[0017] [Table 1] TIFF0007763851000002.tif180150

[0018] In determining which of these eleven compounds or combinations thereof may offer performance advantages over ammonia, aminomethylpropanol (AMP), and monoethanolamine (MEA), each of the eleven compounds was studied for its ability to lift natural color from hair, the degree of damage caused by applying the compound to hair, and the degree of malodor. The results are discussed below.

[0019] In the alkalizing compositions of the present invention, the total amount of all alkanolamine alkalizing agents is typically about 0.001 to 25%, such as about 0.4% to about 20%, such as about 1% to about 15%, such as about 2% to about 12.5%, such as about 3% to about 10%. When ammonium hydroxide is used in combination with the alkanolamines identified herein, the concentration of ammonium hydroxide should be limited to about 0.01% to 14%.

[0020] Oxidative hair dye products In practice, the oxidation hair dye product consists of two containers, the first containing (I) the alkalizing agent composition and the second containing (II) the oxidizing agent composition, which are mixed shortly before application to the hair. The mixture can be called an on-hair product.

[0021] I. Alkalizing Agent Composition The alkalizing agent composition of the present invention comprises an aqueous solution of one or more alkalizing agents and one or more oxidative dyes as shown in Table 1. Optionally, various adjunct ingredients that provide benefits to the alkalizing agent composition or the hair may be included.

[0022] oxidation dyes The alkalizing agent composition according to the present invention comprises one or more primary intermediates that are operable and that impart color to hair when combined with an oxidizing agent. Optionally, the alkalizing agent composition may also comprise one or more couplers.

[0023] Primary intermediates The primary intermediates may generally be present in the alkalizing agent composition in an amount of about 0.001 to 25% by weight, preferably about 0.005 to 20% by weight, and more preferably about 0.01 to 15% by weight of the total alkalizing agent composition. Such primary intermediates include ortho- or para-substituted aminophenols or phenylenediamines, such as para-phenylenediamines of the following formula:

[0024] [ka] (wherein R1 and R2 are each independently hydrogen, C1-6 alkyl, or C1-6 alkyl substituted with a hydroxy group, a methoxy group, a methylsulfonylamino group, a furfuryl group, an aminocarbonyl group, an unsubstituted phenyl group, or an amino-substituted phenyl group; and R3, R4, R5, and R6 are each independently hydrogen, C1-6 alkyl, C1-6 alkoxy, halogen, or C1-6 alkyl substituted with one or more amino groups or hydroxyl groups). Such primary intermediates include para-phenylenediamine (PPD), 2-methyl-1,4-diaminobenzene, 2,6-dimethyl-1,4-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 2,3-dimethyl-1,4-diaminobenzene, 2-chloro-1,4-diaminobenzene, 2-methoxy-1,4-diaminobenzene, 1-phenylamino-4-aminobenzene, 1-dimethylamino-4-aminobenzene, and 1-diethylamino-4-aminobenzene. Suitable primary intermediates include 2-isopropyl-1,4-diaminobenzene, 1-hydroxypropylamino-4-aminobenzene, 2,6-dimethyl-3-methoxy-1,4-diaminobenzene, 1-amino-4-hydroxybenzene, 1-bis(beta-hydroxyethyl)amino-4-aminobenzene, 1-methoxyethylamino-4-aminobenzene, 2-hydroxymethyl-1,4-diaminobenzene, 2-hydroxyethyl-1,4-diaminobenzene, and derivatives thereof, as well as acidic and basic salts thereof. Also suitable are various types of pyrimidines, such as 2,3,4,5-tetraaminopyrimidine sulfate and 2,5,6-triamino-4-pyrimidinol sulfate. Preferred primary intermediates are p-phenylenediamine, p-aminophenol, o-aminophenol, N,N-bis(2-hydroxyethyl)-p-phenylenediamine, 2,5-diaminotoluene, salts thereof, and mixtures thereof.

[0025] Coupler When present, the color coupler may be about 0.0001 to 10% by weight of the total alkalizing agent composition, more preferably about 0.0005 to 8% by weight, and most preferably about 0.001 to 7% by weight. Such color couplers include, for example, compounds represented by the general formula:

[0026] [ka] (wherein R1 is unsubstituted hydroxy or amino, or hydroxy or amino substituted with one or more C1-6 hydroxyalkyl groups; R3 and R5 are each independently hydrogen, hydroxy, amino, or amino substituted with a C1-6 alkyl group, a C1-6 alkoxy group, or a C1-6 hydroxyalkyl group; and R2, R4, and R6 are each independently hydrogen, a C1-6 alkoxy, a C1-6 hydroxyalkyl, or a C1-6 alkyl. Alternatively, R3 and R4 may together form a methylenedioxy group or an ethylenedioxy group. Examples of such compounds include meta-derivatives which may be unsubstituted or substituted on the amino group or benzene ring with an alkyl group, a hydroxyalkyl group, an alkylamino group, or the like, such as phenols, catechol, meta-aminophenols, and meta-phenylenediamines. Suitable couplers include m-aminophenol, 2,4-diaminotoluene, 4-amino, 2-hydroxytoluene, phenylmethylpyrazolone, 1,3-diaminobenzene, 6-methoxy-1,3-diaminobenzene, 6-hydroxyethoxy-1,3-diaminobenzene, 6-methoxy-5-ethyl-1,3-diaminobenzene, 6-ethoxy-1,3-diaminobenzene, 1-bis(beta-hydroxyethyl)amino-3-aminobenzene, 2-methyl-1,3-diaminobenzene, 6-methoxy-1-amino-3-[(beta-hydroxyethyl)amino]-benzene, 6-(beta-aminoethoxy)-1,3-diaminobenzene, 6-(beta-hydroxyethoxy)-1-amino-3-(methylamino)benzene, 6-carboxymethoxy-1,3-diaminobenzene.6-ethoxy-1-bis(beta-hydroxyethyl)amino-3-aminobenzene, 6-hydroxyethyl-1,3-diaminobenzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxy-1-[(beta-hydroxyethyl)amino]benzene, 1-methoxy-2-amino-4-[(beta-hydroxyethyl)amino]benzene, 1-hydroxy-3-(dimethylamino)benzene, 6-methyl-1-hydroxy-3[(beta-hydroxyethyl)amino]benzene, 2,4-dichloro-1-hydroxy-3-aminobenzene, 1-hydroxy-3-(diethylamino)benzene, 1-hydroxy-2-methyl-3-aminobenzene, 2-chloro-6-methyl-1-hydroxy-3-aminobenzene, 1-hydroxy-2-isopropyl-5-methylbenzene, 1,3-dihydroxybenzene, 2-chloro-1,3-dihydroxybenzene, 2- Examples of suitable hydroxybenzoates include methyl-1,3-dihydroxybenzene, 4-chloro-1,3-dihydroxybenzene, 5,6-dichloro-2-methyl-1,3-dihydroxybenzene, 1-hydroxy-3-amino-benzene, 1-hydroxy-3-(carbamoylmethylamino)benzene, 6-hydroxybenzomorpholine, 4-methyl-2,6-dihydroxypyridine, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 6-aminobenzomorpholine, 1-phenyl-3-methyl-5-pyrazolone, 1-hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 5-amino-2-methylphenol, 4-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindole, 6-hydroxyindoline, 2,4-diaminophenoxyethanol, and mixtures thereof.

[0027] Supplementary ingredients Reducing Agents and Antioxidants The alkalizing agent composition may further comprise one or more reducing agents and / or one or more antioxidants. Reducing agents and antioxidants can stabilize the composition by inhibiting the reaction between the primary intermediate and the coupler and the initiation of oxidation upon exposure to atmospheric oxygen. A commonly used reducing agent is sodium metabisulfite, which may be used in a range of 0.1% to 5% by weight of the alkalizing agent composition. Examples of water-soluble antioxidants include erythorbic acid. When the alkalizing agent composition is an emulsion, oil-soluble antioxidants such as t-butylquinone may be useful. Antioxidants typically comprise 0.1% to 5% by weight of the alkalizing agent composition.

[0028] Emollient oil If desired, the alkalizing composition may contain one or more emollient oils. Such oils provide conditioning benefits to hair. When present, such oils may be present in an amount of about 0.001 to 45% by weight of the alkalizing composition, preferably about 0.01 to 40% by weight, and more preferably about 0.1 to 35% by weight. Suitable oils include silicones such as dimethicone, phenylsilicones, fatty alkyl silicones such as cetyl dimethicone or stearyl dimethicone, or silicone surfactants commonly referred to as dimethicone copolyols or cetyl dimethicone copolyol. Also suitable are various animal oils, vegetable oils, or mineral oils derived from plants or animals, or synthetic oils. Examples include oils derived from sunflower, castor seed, orange, lemon, jojoba, and mineral oils.

[0029] surfactants The alkalizing agent composition may contain one or more surfactants. Suitable surfactants include well-known cosmetically acceptable anionic, nonionic, amphoteric, and cationic surfactants. When present, the surfactant may be present in an amount of about 0.001 to 50% by weight, preferably about 0.005 to 45% by weight, and more preferably about 0.1 to 40% by weight of the alkalizing agent composition.

[0030] Polar solvents The alkalizing agent composition may also contain various non-aqueous polar solvents other than water, such as monohydric, dihydric, or polyhydric alcohols and similar water-soluble components. When present, such polar solvents may comprise about 0.01 to 25% by weight of the composition, preferably about 0.05 to 15% by weight, and more preferably about 0.1 to 10% by weight of the first polar solvent. Examples of suitable monohydric alcohols include ethanol, isopropanol, benzyl alcohol, butanol, pentanol, and ethoxyethanol. Examples of dihydric or polyhydric alcohols, as well as sugars and other types of humectants that may be used, include glycerin, glucose, fructose, mannose, mannitol, maltitol, lactitol, and inositol. Suitable glycols include propylene glycol, butylene glycol, ethylene glycol, polyethylene glycols having 4 to 250 repeating ethylene glycol units, and ethoxydiglycol.

[0031] chelating agents The alkalizing agent composition may optionally contain 0.0001-5%, preferably 0.0005-3%, more preferably 0.001-2%, of one or more chelating agents that can complex with and inactivate metal ions to prevent adverse effects of the metal ions on the stability or efficacy of the composition. In particular, the chelating agents chelate metal ions found in water and prevent these ions from interfering with the deposition and reaction of the dye on the hair fiber surface. Suitable chelating agents include EDTA and its calcium, sodium, or potassium derivatives, HEDTA, sodium citrate, TEA-EDTA, and the like.

[0032] pH adjuster It may be desirable to adjust the pH of the alkalizing composition to the desired pH range by adding a small amount of acid or base so that the final on-hair product has a pH of about 8 to about 12. Suitable acids include hydrochloric acid, phosphoric acid, and the like. Suitable bases include sodium hydroxide, ammonium hydroxide, potassium hydroxide, and the like, as well as basic amino acids (arginine, lysine, and histidine). Primary, secondary, or tertiary amines and their derivatives, such as aminomethylpropanol and monoethanolamine, are also suitable. The recommended range for the pH adjuster is about 0.00001 to 8% by weight of the total alkalizing composition, preferably about 0.00005 to 6% by weight, and more preferably about 0.0001 to 5% by weight.

[0033] botanical ingredients The alkalizing agent composition may contain one or more botanical ingredients. If present, the suggested range is about 0.00001-10%, preferably about 0.0001-8%, more preferably about 0.0001-5% by weight of the total alkalizing agent composition. Examples of such ingredients include tea plant (Camellia Sinensis) extract, Camellia Oleifera extract, vanilla extract, green tea extract, and aloe vera (Aloe Barbadensis) extract.

[0034] Container for alkalizing composition The alkalizing agent composition is preferably stored in a container made of an airtight and oxidation-resistant material. Preferably, such a container is in the form of a tube, jar, bottle, or the like. Preferably, the container is a tube, preferably one that can be compressed to dispense the alkalizing agent composition contained therein. Suitable tubes can be metallic. Preferably, the tube is made of oxidation-resistant aluminum. In the most preferred embodiment, the tube is made of oxidation-resistant aluminum having less than 100 ppm of cadmium, mercury, lead, and hexavalent chromium. The closure of the alkalizing agent composition container must prevent air from oxidizing the contents of the container. Various closures are suitable, including, for example, screw caps, snap-off lids, and the like. Preferably, the closure is reusable, for example, in salon environments where multiple uses are desired. Once the container is opened, it can be used to dispense the desired amount of alkalizing agent composition as needed. The container can be resealed and stored for hours, days, weeks, or even months, after which the remaining contents can be used. An alkalizing composition formulated according to the present invention and stored in a suitable container can be used to store the remaining contents indefinitely. For example, the inclusion of an antioxidant in the alkalizing composition allows a container of oxidative hair dye to be stored for 1-6 days, 1-3 weeks, or 1-4 months before it is used again.

[0035] II. Oxidizer Composition The alkalizing agent composition of the present invention is combined with an oxidizing agent composition to form a hair dye composition immediately prior to application to hair. Aqueous oxidizing agents generally contain water in an amount of about 65% to 99% by weight of the oxidizing agent composition, preferably about 70% to 97% by weight, and most preferably about 70% to 94% by weight. Examples of aqueous oxidizing agent compositions include lotions, creams, and gels. Anhydrous oxidizing agent compositions may also be used (e.g., powders). Additionally, the oxidizing agent composition also contains an oxidizing agent that reacts with the precursor dye present in the alkalizing agent composition. In most cases, the oxidizing agent used is hydrogen peroxide, although other peroxides or oxidizing agents, such as calcium peroxide, sodium percarbonate, and one or more persulfates (i.e., ammonia, potassium, and sodium), can be used. Preferably, the hydrogen peroxide concentration in the oxidizing agent composition is about 1 to 20% by weight of the oxidizing agent composition.

[0036] The oxidizer composition may typically include a peroxide stabilizer, such as sodium stannate and pentasodium pentetate. Alternatively, some type of chelating system may be used to maintain a relatively low pH of the oxidizer composition. The stabilizer and / or chelating system may comprise 0.01% to 5.0% by weight of the oxidizer composition. [Example]

[0037] IV. Testing of Alkalizing Agent Compositions The alkanolamines in Table 1 were tested in a base dye composition (without dye or dye precursor) to evaluate their suitability as alkalizing agents. The alkalizing agent compositions according to the invention, as well as control compositions, were subjected to various analytical techniques, such as thermodynamic, optical, and tensile analysis, as well as cytotoxicity testing.

[0038] Hair sample preparation Level 4 mixed-source human hair tresses were purchased from International Hair Importers & Products, Inc. (New York). Testing was performed on untreated hair (control), hair treated with ammonium hydroxide, and hair treated with various single alkalizing agent compounds and their combinations described above. Ten grams of freshly made alkalizing agent composition was mixed with 10 grams of volume 40 (12%) oxidizer developer (Aveda Color Catalyst Conditioning Creme Developer) until a uniform cream was obtained. The ammonium hydroxide sample was also mixed with volume 40 oxidizer developer. Approximately 4 grams of the cream mixture per gram of hair was applied to the sample hair tresses. Each hair tress was then incubated in a 37°C oven for 45 minutes. The hair tresses were rinsed with tap water for 1 minute, after which a 5% SDS (sodium dodecyl sulfate) solution was applied. Each hair tress was massaged in the SDS solution for 30 seconds. The hair tresses were rinsed again with tap water for 1 minute to remove all surfactants. The treated tresses were then dried with a hair dryer at medium / high speed and medium / high heat. The tresses were then air-dried at room temperature for 12 hours before being subjected to differential scanning calorimetry (DSC) and spectrophotometric analysis.

[0039] Alkalizing Agent Compositions Tested The following base alkalizing agent compositions (without dye or dye precursor) were used to test each alkalizing agent or combination thereof:

[0040] [Table 2]

[0041] Table 3 shows the amount of each individual alkalizing agent added to one of the compositions in Table 2 to complete the alkalizing agent composition. The pH, viscosity, and alkalinity of the alkalizing agent compositions are also shown. The viscosity of the formulations was measured using a Brookfield LVD VII Pro Viscometer. Measurements were performed at 22°C using a TF spindle at 6 rpm. All compositions contained the same mole percent alkalizing agent, and the water content was adjusted accordingly. Ammonium hydroxide, the gold standard in alkalizing agents, served as a control, and MEA and AMP, common substitutes for ammonium hydroxide, were included for comparison.

[0042] [Table 3]

[0043] Various binary combinations of alkalizing agents were also tested by combining them in the base compositions shown in Table 2.

[0044] DSC analysis Protein denaturation occurs when proteins lose their secondary, tertiary, or quaternary structure upon application of some external stress or compound, such as a strong acid or base, concentrated inorganic salt, organic solvent (e.g., alcohol or chloroform), or heat, while the peptide bonds between amino acids (primary structure) remain intact. Denaturation of tertiary structure involves disruption of interactions between amino side chains, such as covalent disulfide bridges between cysteine ​​groups, noncovalent dipole-dipole interactions between polar groups, and van der Waals interactions between nonpolar groups in side chains. Denaturation of secondary structure means that proteins lose all regular repeating patterns (e.g., alpha-helical structures and beta-pleated sheets) and adopt a random coil structure.

[0045] It is known that the denaturation of keratin in hair can be detected by differential scanning calorimetry. DSC is a thermal analysis technique used to measure the transition temperature and heat of transition (enthalpy) for endothermic and exothermic reactions. DSC is typically used to measure the melting temperature and solidification temperature at different melting or cooling rates. DSC is sensitive enough to provide information about the molecular weight distribution of polymers.

[0046] Denaturation measurements were performed on untreated hair (control), hair treated with a mixture of ammonium hydroxide and Volume 40 Oxidant Developer (control), and hair treated with various alkalizing compounds (including Volume 40 Oxidant Developer) as described above. For comparison purposes, hair samples treated with NaOH, a very strong alkalizing agent that causes significant damage to human hair above certain concentrations, are also included. NaOH is included as an indicator of the worst level of damage.

[0047] Measurements were performed using a Mettler Toledo DSC822e (Mettler Toledo LLC, Columbus, Ohio) or a Discovery DSC 2500 (TA Instruments, New Castle, Delaware). Experiments were performed under nitrogen protection over a temperature range of 25°C to 180°C at a scan rate of 5°C / min. DSC samples were prepared by cutting and weighing the hair samples (to sizes of 0.1-1.0 mm). The hair samples were mixed with deionized water and then sealed in a high-volume pan for at least 6 hours before measurement. The phase transition temperature (keratin denaturation temperature) of each hair sample was analyzed using either STARe software (Mettler Toledo DSC822e) or TRIOS software (Discovery DSC 2500). Each hair sample was analyzed at least twice, and the average temperature was obtained for data analysis. The higher denaturation temperature indicates that the hair was less damaged as a result of treatment with the mixture of the alkalizing agent composition and the oxidizing agent developer. The results are shown in Tables 4A and 4B.

[0048] [Table 4]

[0049] The above results can be interpreted in terms of structure, intramolecular hydrogen bonding, and shielding of the amine groups. Table 4B lists 13 alkanolamine alkalizing agents in order from lowest to highest denaturation temperature. In order of importance, features that may explain the results are the order of the amine (primary, secondary, tertiary); the number of OH groups, how many carbon atoms the OH group is away from the amine, and whether the nitrogen is adjacent to an OH group and a methyl group.

[0050] [Table 5]

[0051] The above results also show that AP (3-amino-1-propanol) was the only alkalizing agent that caused significantly more damage than both MEA and AMP, which are common substitutes for ammonium hydroxide. Visibly, MEA and AMP caused approximately three times more damage than ammonium hydroxide. Serinol and DMAP performed closest to ammonium hydroxide, making them suitable as total, majority, or partial replacements for ammonium hydroxide, at least with respect to hair denaturation temperature.

[0052] All hair samples treated with the primary amine alkalizing agent compositions (except Tris) exhibit lower denaturation temperatures than samples treated with the ammonium hydroxide compositions, while the hair samples treated with serinol exhibit only slightly lower denaturation temperatures than samples treated with the ammonium hydroxide compositions. However, among the primary amine alkalizing agents, AMPD, AEPD, isoserinol, and serinol perform significantly better than MEA and AMP and can therefore be considered useful for softening and swelling the hair cuticle and allowing penetration of reagents and hair benefit actives into the cortex.

[0053] Among primary amine alkalizing agents, those with two OH groups performed better than those with only one OH group. Within each of these subgroups, the closer the OH group(s) to the amine, on average, the better the performance. Here, the term "closer" means fewer intervening carbon atoms. Also of note is whether the amine is "adjacent" by two or more OH groups within two carbon atoms. The amines in isoserinol and DMAPD are adjacent by two OH groups, but only one of the OH groups is within two carbon atoms.

[0054] The tertiary amine and secondary amine alkalizing agent compositions (TEA, DMAPD, DEA, DMAMP, and DMAP) all caused less damage to hair than the ammonium hydroxide composition. The primary amine alkalizing agent, Tris, also performed well. Among all of these alkalizing agents, those with two or three OH groups performed better than those with only one OH group. Among the secondary and tertiary amine alkalizing agents, those with more OH groups performed better. Tris is a special case. As a primary amine, Tris was expected to perform relatively poorly. However, having all three OH groups within two carbon atoms of the amine and partial proximity appears to have contributed to its performance. TEA caused minimal damage to the tested hair samples, but a residual coating may form on the hair surface. The following generalization can be made: if the aim is to limit damage to the hair, primary alkanolamines with at least two OH groups are preferred, as well as secondary and tertiary alkanolamines.

[0055] It is believed that at least part of the performance of each alkalizing agent can be attributed to stabilization or blocking of the amine group as a result of intramolecular hydrogen bonding, particularly between the hydrogen and nitrogen of the hydroxyl group, but that some other hydrogen bonding or other effect may also be occurring. Indeed, the only difference between AP (the worst performer in the DSC test) and DMAP (a better performer than ammonia) is the two methyl groups on the amine of DMAP, which are believed to stabilize the amine considerably.

[0056] Color Lifting Spectrophotometric methods were used to evaluate the color and appearance changes of various hair samples as a result of exposure to the various alkalizing agent compounds and their combinations described herein. Spectrophotometric methods can be used to measure light reflected from a given surface or object. A Konica Minolta® CM-600d spectrophotometer and its accompanying SpectraMagic NX software were used to collect data for the evaluation of hair tress color. It is standard to express color as three different numerical values ​​(L*, a*, and b*). These values ​​are intended to mimic what the human eye perceives. The a* value, which represents the red / green color of the hair sample, and the b* value, which represents the yellow / blue color of the hair sample, are not reported here. However, the L* value represents the light / dark intensity of the measured surface. The L* value ranges from 0 to 100, with 0 being pure black and 100 being pure white. The higher the L* value, the lighter the hair color and the more effective the alkalizing agent is at lifting natural hair color. L* measurements were performed on untreated hair (control), hair treated with a mixture of ammonium hydroxide and Volume 40 Oxidizer Developer (control), and hair treated with various alkalizing compounds (including Volume 40 Oxidizer Developer) as described above. For comparison purposes, a hair sample treated with NaOH, a very strong alkalizing agent that is expected to induce significant melanin loss above a certain concentration, was also included. Each hair tress was secured at one end to form a swatch with the hair evenly distributed along the binding. The measured L* values ​​are shown in Table 5.

[0057] [Table 6]

[0058] The above results indicate that the isoserinol / oxidant mixture and the 3-amino-1-propanol (AP) / oxidant mixture are superior to the ammonium hydroxide / oxidant mixture (and similar or even superior to NaOH) in lifting natural hair color. Furthermore, isoserinol demonstrated nearly the same efficacy as MEA, two common substitutes for ammonium hydroxide, and significantly superior efficacy to AMP. 3-amino-1-propanol (AP) outperformed all of them. The other compositions were less effective than ammonium hydroxide, MEA, and AMP in lifting hair color. However, AMPD was nearly as good as MEA and ammonium hydroxide. For color lifting, serinol and DMAP, which are comparable to ammonium hydroxide in terms of damage (vis-a-vis), performed significantly worse than ammonium hydroxide. This may suggest the combination of an alkalizing agent, such as ammonia, MEA, or isoserinol, in combination with serinol or DMAP to obtain the benefits of both.

[0059] The color lifting results are nearly the opposite of the DSC results above in that all of the primary amine alkalizing agent compositions performed better than the tertiary amine alkalizing agent compositions, except that Tris performed similarly to the tertiary alkalizing agent DMAP, and the primary amine alkalizing agent AEPD performed similarly to the secondary amine alkalizing agent DEA, although not as well.

[0060] Testing combinations of alkalizing agents The inventors predicted that combinations of alkalizing agents would likely combine the advantages of each while mitigating their drawbacks. Based on the above results, binary combinations of selected alkalizing agents were also tested by combining two alkalizing agent compositions prepared according to Tables 2 and 3. The first set of combinations all contained NH3 as follows: AMPD-NH3, AEPD-NH3, DMAMP-NH3, Tris-NH3, and serinol-NH3. These combinations were tested at different molar ratios, as shown in Tables 6-10 below.

[0061] [Table 7]

[0062] [Table 8]

[0063] [Table 9]

[0064] [Table 10]

[0065] [Table 11]

[0066] [Table 12]

[0067] [Table 13]

[0068] [Table 14]

[0069] [Table 15]

[0070] The addition of AMPD, AEPD, or serinol to NH3 decreased the denaturation temperature, but only slightly. The addition of DMAMP or Tris to NH3 increased the denaturation temperature. Nearly any amount of Tris caused less damage than AMPD, AEPD, or serinol alone, and less damage than AMPD, AEPD, or serinol in combination with NH3. In these combinations containing NH3, the L* values ​​were slightly reduced, indicating lower lifting efficiency than 100% NH3. Tris tended to reduce color-lifting efficacy.

[0071] The denaturation temperature of each mixture of alkalizing agents varies approximately linearly with the relative concentration of each alkalizing agent. The exception is the DMAMP-NH3 combination. In that case, two clusters of data are present (see figure). The first cluster of temperature data occurs between approximately 0 and 15 mole percent of DMAMP. The second cluster occurs between approximately 25 and 100 mole percent of DMAMP. DMAMP-NH3 showed a significant increase in denaturation temperature when going from 100% NH3 to 0.5:99.5 (1:199 DMAMP:NH3). This result was unexpected. This nonlinear relationship indicates a range of mole percents where color lifting increases with little further denaturation. Therefore, we naturally expect favorable results for molar ratios between 100% NH3 and 3:7 (DMAMP:NH3). For example, molar ratios (DMAMP:NH3) of 1:199, 1:99, 1:90, 1:45, 1:30, 1:22.5, 1:18, 1:15, 1:12.9, 1:11.25, 1:3, and 1:2.5 are useful because they are significantly less damaging than 100% NH3. Molar ratios of 1:99 to 1:2.5 are preferred; 1:45 to 1:4 are more preferred; and molar ratios of 1:20 to 1:3 are even more preferred.

[0072] Overall, the above data suggests that there is a preferred range of relative concentrations for each combination of alkalizing agents, depending on the effect desired. A summary of the DSC results is shown in Table 14. Also shown are preferred ranges of molar ratios for each combination of alkalizing agents, based solely on the DSC results, and based on the DSC results and the L* values.

[0073] [Table 16]

[0074] cytotoxicity The effects of alkalizing agent compositions on outer root sheath cells and keratinocytes were evaluated. The MultiTox-Fluor Multiplex Cytotoxicity Assay (Promega Corp., Madison, Wisconsin) simultaneously measures two protease activities: one as a marker of cell viability and the other as a marker of cytotoxicity. This assay measures the response of outer root sheath cells and keratinocytes to various concentrations of alkalizing agent, determining the IC, the concentration that elicits a mid-height response (halfway between the baseline and maximum responses). 50 In this study, a larger IC 50 The values ​​indicate that the alkalinizing agent induces less stress on the cells. The results are shown in Table 15.

[0075] [Table 17]

[0076] For both cell types, the conventional ammonia substitutes MEA and AMP were more toxic to cells than ammonium hydroxide. DMAMP was also more toxic than ammonium hydroxide, but less toxic than the conventional ammonia substitute AMP and less toxic to keratinocytes than MEA. Furthermore, for both cell types, AMPD, AEPD, DMAPD, and isoserinol were significantly less toxic than ammonium hydroxide.

[0077] Tensile strength The effect of alkalizing agent compositions on the tensile strength of hair fibers was measured. Hair tresses were treated with the compositions shown in Tables 2 and 3 above. From each tress, several individual hair fibers were threaded and crimped using brass crimps and a Diastron AAS 1600 (Diastron Ltd, UK) to prepare them for tensile analysis. The average cross-sectional area of ​​each fiber was determined using a laser micrometer FDAS 770 unit (Diastron Ltd, UK) at 24°C and 55% relative humidity (RH). All hair fibers were pulled to break using a Diastron MTT686 device with a control unit UV1000 (Diastron Ltd, UK). Final results were calculated using software analysis (UvWin 2.35.0000, Diastron, Ltd, UK). The average applied stress at break is shown in Table 16. A greater stress at break indicates that the hair fiber was less weakened by the applied alkalizing agent composition.

[0078] [Table 18]

[0079] The tensile data in Table 16 show the average break stress for hair fibers after treatment with an alkalizing composition and an oxidizing agent. Samples are compared to NH3 as a baseline. The break stress data show a general trend of decreasing damage when going from primary to tertiary amines. For example, tertiary amines (DMAMP, DMAP, DMAPD, TEA) result in similar or lower amounts of damage than their primary amine analogs (AMP, AP, AMPD, MEA). Going from primary to secondary to tertiary also reduces the amount of damage seen with MEA, DEA, and TEA. Furthermore, the data above also show that the position and number of hydroxyl groups affect tensile strength, as seen when comparing AP vs. AMP vs. AMPD. The introduction of two hydroxyl groups (AMPD) surprisingly results in less damaged hair fibers. A similar effect is observed when using Tris, a primary amine flanked by three hydroxyl groups. Both of these examples show similar fiber damage to NH3, along with comparable lift.

[0080] Odor Evaluation An expert perfumer ranked several of the alkalizing agent compositions presented in Tables 1 and 2. A base formulation without alkalizing agent (Table 1) was used as a control. Among the primary alkanolamine compositions, the ranking from no malodor to strongest malodor is: Control > AMPD = Serinol > Tris > MEA = AMP > AEPD > NH3 and among the tertiary alkanolamine compositions, the order from no malodor to strongest malodor is: Control > DMAMP > DMAPD > NH3 It was.

[0081] All alkanolamine compositions evaluated were less malodorous than the ammonium hydroxide composition. Among the primary amines, AMPD, serinol, and tris performed better than two traditional ammonia substitutes, MEA and AMP. The two tertiary amines tested did not perform as well as MEA and AMP.

[0082] [Table 19]

[0083] In summary, six of the 11 alkanolamines performed well in DSC analysis, suggesting reduced hair fiber damage compared to ammonium hydroxide. In tensile tests, eight of the 11 alkanolamines performed comparable to NH3. In DSC analysis, 10 of the 11 alkanolamines demonstrated reduced hair fiber damage compared to MEA and AMP, traditional ammonium hydroxide alternatives, when used as hair colorant alkalizers. In tensile strength analysis, eight of the 11 alkanolamines demonstrated reduced hair fiber damage compared to MEA and AMP when used as hair colorant alkalizers. Three alkanolamines were superior to ammonium hydroxide in lifting color from hair. One of these (isoserinol) was significantly superior to AMP and nearly equivalent to MEA in lifting hair color. Furthermore, combinations of 11 alkalizing agents with or without ammonium hydroxide were found to be advantageous in terms of reducing hair damage, improving color lifting, or both. The inventors found that for mixtures of two alkalizing agents, the keratin denaturation temperature varied approximately linearly with the relative concentration of each alkalizing agent, except in the case of DMAMP-NH3. This result was unexpected. This, combined with the L* value measurements, suggested the existence of preferred ranges of relative concentrations for each combination of alkalizing agents, and the inventors identified these ranges.

[0084] Primary alkanolamines have a better odor than tertiary alkanolamines. MEA, AMP, and DMAMP are more toxic to outer root sheath cells and keratinocytes than ammonium hydroxide. However, AMPD, AEPD, DMAPD, and isoserinol are significantly less toxic to both types of cells than ammonium hydroxide. Some or all of these properties may be advantageous in both oxidative and non-oxidative hair treatments.

[0085] In general, the inventors have demonstrated the suitability of various alkanolamines for softening and swelling the hair cuticle, allowing agents and hair benefit actives to penetrate the cortex. These results are useful for various types of hair treatment applications, but the inventors have shown this is particularly true for hair color treatments. The inventors have shown that depending on the type of hair coloring application, the use of ammonium hydroxide can be reduced or eliminated.

[0086] Consideration Based on this observation, it can be speculated that intramolecular hydrogen bonds in alkanolamines result in a conformation that provides some degree of amine stabilization. Most interesting are hydrogen bonds between the nitrogen atom of the alkanolamine and one or more hydroxyl groups. This type of intramolecular bond provides an explanation for the variations observed by the inventors regarding hair fiber modification and color lifting. Generally, the more hydrogen bonds the amine involves, the less damage the hair experiences, but at the cost of less effective color lifting. However, of particular interest are alkanolamine molecules in which the electron bond donor is located exactly two carbon atoms away from the nitrogen atom. Primary alkanolamines with two or more hydroxyl groups located at the C2 position are useful alkalizing agents in hair treatment products. Similarly, secondary and tertiary alkanolamines with at least one hydroxyl group located at the C2 position are also useful.

[0087] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention. The present invention includes, for example, the following embodiments. [Section 1] An alkalizing agent composition comprising one or more primary intermediates and / or couplers, ammonia and 2-amino-2-methyl-1,3-propanediol, wherein the molar ratio of 2-amino-2-methyl-1,3-propanediol to ammonia is 1:1 to 1:9. [Section 2] An alkalizing agent composition comprising one or more primary intermediates and / or couplers, ammonia and 2-amino-2-ethyl-1,3-propanediol, wherein the molar ratio of 2-dimethyl-amino-2-methyl-1-propanol to ammonia is 1:1 to 1:3. [Section 3] An alkalizing agent composition comprising one or more primary intermediates and / or couplers, ammonia and 2-dimethyl-amino-2-methyl-1-propanol, wherein the molar ratio of 2-dimethyl-amino-2-methyl-1-propanol to ammonia is 1:4 to 1:199. [Section 4] An alkalizing agent composition comprising one or more primary intermediates and / or couplers, ammonia and Tris, wherein the molar ratio of Tris to ammonia is 1:9 to 2:1. [Section 5] An alkalizing agent composition comprising one or more primary intermediates and / or couplers, ammonia and serinol, wherein the molar ratio of serinol to ammonia is 1:2.5 to 1:9. [Section 6] An alkalizing agent composition comprising one or more primary intermediates and / or couplers, 2-amino-2-methyl-1,3-propanediol, and Tris, wherein the molar ratio of 2-amino-2-methyl-1,3-propanediol to Tris is 9:1 to 1:99. [Section 7] An alkalizing agent composition comprising one or more primary intermediates and / or couplers, 2-amino-2-ethyl-1,3-propanediol, and Tris, wherein the molar ratio of 2-amino-2-ethyl-1,3-propanediol to Tris is 9:1 to 1:99. [Section 8] An alkalizing agent composition comprising one or more primary intermediates and / or couplers, serinol, and tris, wherein the molar ratio of serinol to tris is 9:1 to 1:99. [Section 9] An alkalizing agent composition comprising one or more primary intermediates and / or couplers, and serinol. [Section 10] An alkalizing agent composition comprising one or more primary intermediates and / or couplers, and 3-dimethyl-amino-1-propanol. [Section 11] 1. A hair dye product comprising a first container and a second container comprising: a first container containing an alkalizing agent composition comprising one or more primary intermediates and / or couplers, and serinol; a second container containing an oxidizer composition; The hair dye product. [Section 12] Item 12. The hair dye product according to Item 11, wherein the product has a pH of 8 to 12. [Section 13] 1. A hair dye product comprising a first container and a second container comprising: a first container containing one or more primary intermediates and / or couplers, and an alkalizing agent composition containing 3-dimethyl-amino-1-propanol; a second container containing an oxidizer composition; The hair dye product. [Section 14] Item 14. The hair dye product according to Item 13, wherein the product has a pH of 8 to 12.

Claims

1. 1. An alkalizing agent composition comprising one or more primary intermediates and / or couplers, ammonia and serinol, wherein the molar ratio of serinol to ammonia is from 1:2.5 to 1:

9.

2. 1. An alkalizing agent composition comprising one or more primary intermediates and / or couplers, 2-amino-2-methyl-1,3-propanediol, and Tris, wherein the molar ratio of 2-amino-2-methyl-1,3-propanediol to Tris is from 9:1 to 1:

99.

3. 1. An alkalizing agent composition comprising one or more primary intermediates and / or couplers, 2-amino-2-ethyl-1,3-propanediol, and Tris, wherein the molar ratio of 2-amino-2-ethyl-1,3-propanediol to Tris is from 9:1 to 1:

99.

4. 1. An alkalizing agent composition comprising one or more primary intermediates and / or couplers, serinol, and tris, wherein the molar ratio of serinol to tris is from 9:1 to 1:

99.

5. An alkalizing agent composition comprising one or more primary intermediates and / or couplers, and serinol.

6. An alkalizing agent composition comprising one or more primary intermediates and / or couplers, and 3-dimethyl-amino-1-propanol.

7. 1. A hair dye product comprising a first container and a second container: a first container containing an alkalizing agent composition comprising one or more primary intermediates and / or couplers, and serinol; a second container containing an oxidizer composition; The hair dye product.

8. 8. The hair dye product of claim 7, wherein the product has a pH of 8 to 12.

9. 1. A hair dye product comprising a first container and a second container: a first container containing one or more primary intermediates and / or couplers, and an alkalizing agent composition containing 3-dimethyl-amino-1-propanol; a second container containing an oxidizer composition; The hair dye product.

10. 10. The hair dye product of claim 9, wherein the product has a pH of 8 to 12.

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