Hair treatment composition with amine derivatives

Abstract

The use of certain alkanolamines in hair treatment compositions as a partial or complete replacement for ammonium hydroxide is disclosed. When used as alkalizing agents in hair dyes, these derivatives exhibit reduced hair fiber damage, effective color enhancement, and significant improvements in cytotoxicity and odor compared to known alternatives to ammonium hydroxide.

Description

[0001] This application is a divisional application of the invention patent application with application number 202280039307.5, application date March 30, 2022, entitled "Hair Treatment Composition Containing Amine Derivatives".

[0002] This application claims the benefit and priority of U.S. Patent Application No. 63 / 169507, filed April 1, 2021, and U.S. Patent Application No. 17 / 656998, filed March 29, 2022, the full text of which is incorporated herein by reference. Invention Field

[0003] This invention belongs to the field of hair treatment applications. Specifically, it relates to an alternative to ammonium hydroxide for softening and swelling the hair cuticle and enabling the reagent and hair-beneficial active ingredients to penetrate into the cortex.

[0004] background Hair structure Human hair fibers are generally understood to have an outermost layer called the cuticle. The cuticle contains approximately 6-12 overlapping layers of flattened keratinocytes arranged in a "fish scale" pattern along the longitudinal direction of the hair fiber. This overlapping cell arrangement allows cells to glide over each other, giving the hair fiber a high degree of flexibility and preventing breakage. The cuticle also regulates the amount of water within the hair shaft. The outermost surface of the cuticle is coated with lipids that make the hair surface hydrophobic. Furthermore, the fish scale arrangement and lipid coating of the cuticle give the hair fiber barrier properties. The second layer of the hair fiber beneath the cuticle is the cortex. Here, a natural dye called melanin is present. Due to the translucent nature of the cuticle, melanin in the cortex is usually visible. The cells of the cortex form a matrix that supports the structure of keratin proteins. In the cortex, filaments of protein composed of long keratin chains are the main structural components of hair. These keratin chains are rich in the sulfur-containing amino acid cysteine, which forms permanent, thermally stable cross-links between the keratin chains in the form of disulfide bridges. Human hair is approximately 14-20% cysteine. The extensive disulfide bonds of cysteine ​​contribute about one-third of the strength to hair and make it generally insoluble except in specific dissociating or reducing agents.

[0005] soften the stratum corneum This invention relates to softening and swelling the hair cuticle for any purpose, such as, but not limited to, loosening, straightening, perming, strengthening, and dyeing the hair. Ammonia (in solution) is considered the "gold standard" in various types of hair treatments where swelling and loosening of the cuticle are required. Ammonium hydroxide (an alkalizing agent) raises the pH of the hair, causing the hair cuticle to swell and loosen, allowing active substances and / or reagents to penetrate the hair. However, the use of ammonia has many disadvantages. For example, ammonia gas readily escapes into the surrounding environment during use, releasing a strong odor and irritating the skin, eyes, nose, and throat. These adverse effects can be experienced by the person treating the hair and by the person providing the treatment. Furthermore, ammonia is known to damage hair by breaking peptide bonds. For this reason, research into alternative cuticle penetration methods has been conducted for decades with mixed results. For example, aminomethylpropanol (AMP) and monoethanolamine (MEA) have been used as alternatives to ammonium hydroxide due to their low odor. Both molecules are known to be used as pH buffers in cosmetic preparations. Regarding its effect on hair, the amine functional group NH2 reacts similarly to ammonia (NH3) in ammonium hydroxide solution, while significantly reducing the odor of ammonia. However, a significant increase in hair fiber damage is associated with AMP and MEA, and this remains a major problem in the field. In fact, until now, 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 foul odor and excessive hair damage.

[0006] hair dyeing treatment Although the principles of the present invention can be applied to various types of hair treatments, the present invention is described herein in relation to hair dyeing treatments.

[0007] Hair coloring is a very popular cosmetic procedure. Currently, based on color retention, there are four basic types of hair coloring treatments. Temporary and semi-permanent are non-oxidative treatments that involve depositing colored dyes onto the surface of the hair cuticle. Temporary hair coloring is used to color hair for a short period, such as one day. This type of hair color can be achieved using basic dyes, acid dyes, disperse dyes, pigments, or metallized dyes. Temporary dyes cannot penetrate the hair due to their molecular size and have little affinity for hair; they are typically washed out with a single wash. In contrast, semi-permanent dye molecules are smaller and exhibit some affinity for hair. The smaller size allows the dye to penetrate into the cuticle, and some dye may even reach the cortex. However, alkalizing agents are sometimes used in semi-permanent treatments to promote penetration through the cuticle. For this reason, the present invention can be used for semi-permanent hair coloring. As a result of penetration into the cuticle, semi-permanent dyes require approximately six to twelve washes to remove. Temporary and semi-permanent hair coloring products are available as washes, gels, shampoos, liquid solutions, lotions, and mousses.

[0008] Permanent hair coloring treatments provide color that cannot be washed out of hair and effectively lasts until the treated hair grows out. The "dye" in commercial coloring products is actually a colorless dye precursor, small enough to migrate and diffuse into the cortex beneath the swollen cuticle. Inside the hair cortex, the precursor undergoes a series of redox reactions to reveal the final color. In the field of oxidative 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 coupling agents or secondary intermediates). By design, the redox potential of the primary intermediate is more favorable for oxidation than that of the secondary intermediate, so that the primary intermediate will be oxidized first. A weaker oxidation potential means that a secondary intermediate alone can only produce a slight color, but can be used to contribute highlights. The primary intermediate is oxidized into a highly reactive class, which continues to react with electron-rich secondary intermediates to form a colorless transient intermediate called a leuco dye. The leuco dye is rapidly oxidized into the final colored conjugated dye. Due to their size, the conjugated dye molecules are resistant to rinsing out of the cortex.

[0009] Typically, major and minor intermediates fall into three aromatic types: aromatic diamines, aminophenols, and phenols. Major intermediates are aromatic diamines and aminophenols, where the substituted amino or hydroxyl group is located at the para or ortho position relative to the amino group. This orientation provides a property of easy oxidation. Major intermediates can form quinone, semiquinone, and imin-quinone structures. Examples of compounds found to be usable as major 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-phenylenediamine, etc. Common modifiers are aromatic m-diamines, m-aminophenols, and m-polyphenols. These molecules are less readily oxidized when substituents are present at the meta position. Examples include: m-phenylenediamine, 2,4-resorcinol-diaminoanisole, m-chlororesorcinol, m-aminophenol, resorcinol, 2-methylresorcinol, 1-naphthol, 4-amino-2-hydroxytoluene, and 1,3-phenylenediamine.

[0010] The other two basic components of an oxidative hair dye system are an alkalizing agent and an oxidizing agent. Both perform 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. Furthermore, the alkalizing agent raises the pH of the cortical environment (to approximately pH 9-11), which enhances the reactivity of the oxidizing agent. The oxidizing agent (also known as a color developer, usually hydrogen peroxide H₂O₂) oxidizes the main intermediate to initiate a cascade oxidation reaction that converts the colorless precursor dye into the final colored complex. However, simultaneously, the alkalizing agent converts a portion of the H₂O₂ into OOH. - OOH - It is a highly reactive bleaching agent that neutralizes natural hair melanin or any previously applied oxidative hair color, allowing the newly applied color to appear without distortion.

[0011] Incompletely permanent hair coloring is another treatment in which this invention will find application. Incompletely permanent hair coloring (Demi-permanent hair color), which lasts approximately 20-24 shampoo cycles, occupies an intermediate position between semi-permanent and permanent hair coloring. Incompletely permanent hair coloring treatments use a mixture of semi-permanent dyes and dye precursors typical of permanent coloring treatments. The dye is mixed with an alkalizing agent (such as monoethanolamine MEA or aminomethylpropanol AMP), which is less efficient at swelling the cuticle than ammonia. The colorless dye precursor penetrates the outer cuticle, and a portion is able to enter the cortex, where the precursor molecules subsequently bind to produce larger colored molecules that resist rinsing. Hydrogen peroxide is used, as in permanent coloring, but at a lower concentration. As a result, the pre-existing hair color is not significantly enhanced. Therefore, this type of dye is well-suited for adding deeper colors to hair. Invention Overview This invention relates to compositions and methods for softening and swelling the hair cuticle. The compositions contain certain amine derivatives characterized by electron donors / acceptors, making them suitable as keratin-compatible alkalizing agents for softening and swelling the hair cuticle.

[0013] Overview of the attached figures The only figure shows data on the denaturation temperature of the alkalizing agent composition containing a combination of 2-dimethyl-amino-2-methyl-1-propanol (DMAMP) and NH3.

[0014] Detailed description Unless otherwise explicitly stated, all concentrations of materials and reaction conditions should be understood as being modified by the word “approximately”.

[0015] Unless otherwise stated, all concentrations are expressed as a weight percentage of the final composition.

[0016] The term "includes" means that the list of elements is not limited to those explicitly listed.

[0017] The specific embodiments described herein are merely illustrative, and the invention is not limited to those mentioned embodiments.

[0018] Alkalizing agent It can be demonstrated that certain C3-C6 alkanolamines (as applicable), characterized by electron donor / acceptor properties, can be used alone or in combination as alkalizing agents in oxidative and non-oxidative hair coloring applications. Alkanolamines consist of an alkane backbone with amino and hydroxyl functional groups. These relatively large organic molecules are not as volatile as ammonia. However, like ammonia, alkanolamines can generally produce a strongly alkaline environment that can potentially damage hair and skin cells. The amine group is generally considered to be the cause of hair damage. In fact, depending on the concentration required to reproduce the benefits of ammonia in hair treatment applications, some alkanolamines can produce odors and damage similar to ammonia. Here, eleven alkalizing agents of particular interest are shown in Table 1 (excluding ammonium hydroxide, MEA, and AMP, which are included for comparison only).

[0019] In determining which of these eleven compounds, or combinations thereof, would provide superior performance benefits compared to ammonia, aminomethylpropanol (AMP), and monoethanolamine (MEA), the ability of each of the eleven compounds to remove natural color from hair, the degree of damage caused by applying the compound to the hair, and the degree of malodor were investigated. These results are discussed below.

[0020] In the alkalizing compositions of the present invention, the total amount of all alkanolamine alkalizing agents will typically be from about 0.001% to 25%; for example, from about 0.4% to about 20%; for example, from about 1% to about 15%; for example, from about 2% to about 12.5%; for example, from about 3% to about 10%. If ammonium hydroxide is used in combination with the alkanolamines identified herein, the concentration of ammonium hydroxide should be limited to from about 0.01% to 14%.

[0021] Oxidative hair dye products In practice, oxidative hair dye products consist of two containers: the first contains an (I) alkalizing agent composition, and the second contains an (II) oxidizing agent composition. These are mixed shortly before application to the hair. The mixture may be referred to as an on-hair product.

[0022] I. Alkaliizing agent composition The alkalizing agent composition of the present invention comprises an aqueous solution of one or more alkalizing agents and one or more oxidizing dyes shown in Table 1. Optionally, various auxiliary ingredients may be included to provide benefits to the alkalizing agent composition or to the hair.

[0023] Oxidized dyes The alkalizing agent composition according to the invention comprises one or more major intermediates that, when combined with an oxidizing agent, can function to impart hair color. Optionally, the alkalizing agent composition may also comprise one or more coupling agents.

[0024] main intermediate The primary intermediate is typically 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, more preferably about 0.01 to 15% by weight. Such primary intermediates include ortho- or para-substituted aminophenols or phenylenediamines, such as p-phenylenediamine of the following formula: R1 and R2 are each independently hydrogen and C. 1-6 Alkyl, or phenyl-substituted with hydroxyl, methoxy, methanesulfonylamino, furfuryl, aminocarbonyl, unsubstituted phenyl, or amino-substituted phenyl C 1-6 Alkyl group; and R3, R4, R5 and R6 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Alkoxy, halogen, or C substituted with one or more amino or hydroxyl groups 1-6Alkyl groups. Key intermediates of this class include p-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, 2-isopropyl-1,4-diaminobenzene, 1-hydroxypropylamino-4-aminobenzene, 2,6-dimethyl-3-methoxy-1,4-diaminobenzene, 1-amino-4-hydroxybenzene, 1-bis(β-hydroxyethyl)amino-4-aminobenzene, 1-methoxyethylamino-4-aminobenzene, 2-hydroxymethyl-1,4-diaminobenzene, 2-hydroxyethyl-1,4-diaminobenzene and their derivatives, and their acidic or basic salts. 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, their salts, and mixtures thereof.

[0025] Coupling agent If present, the colored coupling agent may be about 0.0001-10% by weight of the total alkalizing agent composition, more preferably about 0.0005-8% by weight, and most preferably about 0.001-7% by weight. Such colored coupling agents include, for example, those having the following general formula: Where R1 is an unsubstituted hydroxyl or amino group, or is substituted by one or more C1 groups. 1-6 Hydroxyl-substituted hydroxyl or amino group; R3 and R5 are each independently hydrogen, hydroxyl, amino, or C-substituted. 1-6 Alkyl, C 1-6 Alkoxy or C 1-6 A hydroxyalkyl-substituted amino group; and R2, R4, and R6 are each independently hydrogen, C 1-6 Alkoxy, C 1-6 Hydroxyalkyl, or C 1-6Alkyl groups. Alternatively, R3 and R4 together can form methylenedioxy or ethylenedioxy groups. Examples of such compounds include meta-derivatives such as phenol, catechol, m-aminophenol, m-phenylenediamine, etc., which may be unsubstituted or substituted with alkyl, hydroxyalkyl, alkylamino, etc., on the amino or benzene ring. Suitable coupling agents include m-aminophenol, 2,4-diaminotoluene, 4-amino-2-hydroxytoluene (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(β-hydroxyethyl)amino-3-aminobenzene, 2-methyl-1,3-diaminobenzene, 6-methoxy-1-amino-3-[(β-hydroxyethyl)amino]-benzene, 6-(β-aminoethoxy)-1,3- Diaminobenzene, 6-(β-hydroxyethoxy)-1-amino-3-(methylamino)benzene, 6-carboxymethylmethoxy-1,3-diaminobenzene, 6-ethoxy-1-bis(β-hydroxyethyl)amino-3-aminobenzene, 6-hydroxyethyl-1,3-diaminobenzene, 3,4-methylenedioxyphenol, 3,4-methylenedioxy-1-[(β-hydroxyethyl)amino]benzene, 1-methoxy-2-amino-4-[(β-hydroxyethyl)amino]benzene, 1-hydroxy-3-(dimethylamino)benzene, 6-methyl-1-hydroxy-3 -[(β-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-methyl-1,3-dihydroxybenzene, 4-chloro-1,3-dihydroxybenzene, 5,6-dichloro-2-methyl-1,3-dihydroxybenzene, 1-hydroxy-3-aminobenzene 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-hydroxydihydroindole, 6-hydroxyindole, 6-hydroxydihydroindole, 2,4-diaminophenoxyethanol, and mixtures thereof.

[0026] auxiliary ingredients reducing agents and antioxidants The alkalizing agent composition may further comprise one or more reducing agents and / or one or more antioxidants. The reducing agents and antioxidants stabilize the composition by inhibiting the reaction between the main intermediate and the coupling agent, as well as oxidation initiated by exposure to atmospheric oxygen. A commonly used reducing agent is sodium metabisulfite, which may be used at 0.1% to 5% by weight of the alkalizing agent composition. Water-soluble antioxidants include isoascorbic acid. If the alkalizing agent composition is an emulsion, oil-soluble antioxidants such as tert-butylbenzoquinone may be used. Antioxidants typically comprise 0.1% to 5% by weight of the alkalizing agent composition.

[0027] Moisturizing oil If desired, the alkalizing agent composition may contain one or more moisturizing oils. Such oils will provide a conditioning effect on the hair. If present, such oils may constitute about 0.001% to 45% by weight of the alkalizing agent composition, preferably about 0.01% to 40%, more preferably about 0.1% to 35%. Suitable oils include silicones such as polydimethylsiloxane, phenyl silicone, fatty alkyl silicones such as cetyl or stearyl polydimethylsiloxane, or silicone surfactants commonly referred to as polydimethylsiloxane copolyols or cetyl polydimethylsiloxane copolyols. Also suitable are various animal, plant, or mineral oils derived from plants or animals, or synthetic oils. Examples include oils from sunflower, castor seed, orange, lemon, jojoba, mineral oil, etc.

[0028] surfactants The alkalizing agent composition may contain one or more surfactants. Suitable surfactants include well-known cosmetic-grade anionic, nonionic, amphoteric, and cationic surfactants, etc. If present, the surfactant may be about 0.001-50% by weight of the alkalizing agent composition, preferably about 0.005-45%, more preferably about 0.1-40%.

[0029] polar solvents The alkalizing agent composition may also contain various non-aqueous polar solvents other than water, including monohydric alcohols, dihydric alcohols, or polyhydric alcohols, and similar water-soluble components. If present, such polar solvents may constitute about 0.01-25% by weight of the first composition of polar solvents, preferably about 0.05-15%, more preferably about 0.1-10%. Examples of suitable monohydric alcohols include ethanol, isopropanol, benzyl alcohol, butanol, pentanol, ethoxyethanol, etc. Examples of dihydric alcohols or polyhydric alcohols, as well as sugars and other types of humectants that may be used, include glycerin, glucose, fructose, mannose, mannitol, maltitol, lactitol, inositol, etc. Suitable diols include propylene glycol, butanediol, ethylene glycol, polyethylene glycol having 4 to 250 repeating ethylene glycol units, ethoxydiethylene glycol, etc.

[0030] 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 capable of complexing with and deactivating metal ions to avoid their adverse effects on the stability or effectiveness of the composition. In particular, the chelating agent chelates metal ions present in water and prevents these ions from interfering with the deposition and reaction of dye with the surface of hair fibers. Suitable chelating agents include EDTA and its calcium, sodium, or potassium derivatives, HEDTA, sodium citrate, TEA-EDTA, etc.

[0031] pH adjuster It is also desirable to add a small amount of acid or base to adjust the pH of the alkalizing agent composition to the desired pH range, so that the final hair care product has a pH of approximately 8 to approximately 12. Suitable acids include hydrochloric acid, phosphoric acid, etc. Suitable bases include sodium hydroxide, ammonium hydroxide, potassium hydroxide, etc., as well as basic amino acids (arginine, lysine, and histidine). Primary, secondary, or tertiary amines and their derivatives, such as aminomethylpropanol, monoethanolamine, etc., are also suitable. The recommended range for pH adjusters is approximately 0.00001-8% by weight of the total alkalizing agent composition, preferably approximately 0.00005-6%, more preferably approximately 0.0001-5%.

[0032] Plant ingredients The alkalizing agent composition may contain one or more plant-based ingredients. If present, the recommended range is about 0.00001-10% by weight of the total alkalizing agent composition, preferably about 0.0001-8%, more preferably about 0.0001-5%. Examples of such ingredients include tea tree extract, camellia oil extract, vanilla extract, green tea extract, aloe vera extract, etc.

[0033] Container for alkalizing composition The alkalizing agent composition is preferably stored in an airtight container made of an oxidation-resistant material. Such containers are preferably in the form of tubes, cans, bottles, etc. Preferably, the container is a tube, preferably a tube that can be compressed to dispense the alkalizing agent composition contained therein. Suitable tubes may 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 container for the alkalizing agent composition must prevent air oxidation of the contents of the container. Various closures are suitable, including screw caps, snap caps, etc. Preferably, in cases requiring multiple uses, such as in a beauty salon environment, the closure is reusable. Once the container is opened, it can be used to dispense the required amount of the alkalizing agent composition as needed. The container can be resealed and stored for hours, days, weeks, or even months before the remaining contents are used. Alkalizing agent compositions formulated according to the invention and stored in suitable containers can be used, and the remaining contents can be stored indefinitely. For example, including an antioxidant in an alkalizing agent composition will allow the container of the oxidative hair dye to be used and stored for 1-6 days, 1-3 weeks, or 1-4 months before reuse.

[0034] II. Oxidizing agent composition Before application to hair, the alkalizing agent composition of the present invention is combined with the oxidizing agent composition to form a hair dyeing composition. The aqueous form of the oxidizing agent composition contains water, typically in an amount of about 65% to 99% by weight of the oxidizing agent composition, preferably about 70% to 97%, and most preferably about 70% to 94%. The aqueous form of the oxidizing agent composition may include lotions, creams, and gels. Sometimes anhydrous forms of the oxidizing agent composition (e.g., powders) are used. Furthermore, the oxidizing agent composition also contains an oxidizing agent that will react with the precursor dye present in the alkalizing agent composition. Most commonly, the oxidizing agent used is hydrogen peroxide, but other peroxides or oxidizing agents, such as calcium peroxide, sodium percarbonate, and one or more persulfates (i.e., ammonia, potassium, and sodium), may be used. Preferably, the concentration of hydrogen peroxide in the oxidizing agent composition is about 1 to 20% by weight of the oxidizing agent composition.

[0035] Oxidant compositions typically include peroxide stabilizers such as sodium stannate and pentasodium pentate. Alternatively, some type of chelation system may be used to maintain a relatively low pH in the oxidant composition. The stabilizer and / or chelation system may comprise 0.01% to 5.0% of the weight of the oxidant composition.

[0036] IV. Testing of Alkaliizing Agent Compositions The alkanolamines listed in Table 1 were tested in a base dye composition (containing neither dye nor dye precursor) to assess their suitability as alkalizing agents. Various analytical techniques, including thermodynamic, optical, and tensile analyses, and cytotoxicity tests, were applied to the alkalizing agent compositions according to the invention and control compositions.

[0037] Hair sample preparation Grade 4 mixed source human hair strands were purchased from International Hair Importers & Products, Inc (New York). Raw hair (control), hair already treated with ammonium hydroxide, and hair already treated with various single alkalizing agent compounds and combinations thereof as described herein were tested. 10 g of freshly prepared alkalizing agent composition was mixed with 10 g (v / v) of 40 (12%) Aveda Color Catalyst Conditioning Crème Developer until a uniform cream was obtained. The ammonium hydroxide sample was also mixed with 40 v / v of the oxidizing agent developer. Approximately 4 g of the cream mixture per gram of hair was applied to the sample hair strand. Each strand was then incubated in a 37°C oven for 45 minutes. The hair strands were rinsed with tap water for 1 minute, followed by application of a 5% SDS (sodium lauryl sulfate) solution. Each strand was massaged in the SDS solution for 30 seconds. The hair strands were rinsed again with tap water for 1 minute to remove all surfactants. The treated hair strands were blow-dried at medium / high speed using medium / high heat. Afterward, the hair strands were air-dried at room temperature for 12 hours, followed by differential scanning calorimetry (DSC) and spectrophotometric analysis.

[0038] The tested alkalizing agent composition Each alkalizer or combination thereof was tested using the following basic alkalizer compositions (without dye or dye precursor).

[0039] 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 LVDVII Pro viscometer. Measurements were performed at 22°C with a TF rotor at 6 rpm. All compositions contained the same molar percentage of alkalizing agent, with the water content adjusted accordingly. Ammonium hydroxide, the gold standard among alkalizing agents, was used as a control, and MEA and AMP, common alternatives to ammonium hydroxide, were included for comparison.

[0040] They were also tested by incorporating various binary combinations of alkalizing agents into the base compositions shown in Table 2.

[0041] DSC analysis Protein denaturation occurs when proteins lose their secondary, tertiary, or quaternary structures by applying external stress or compounds, such as strong acids or bases, concentrated inorganic salts, organic solvents (e.g., alcohols or chloroform), or heat, while the peptide bonds between amino acids (primary structure) remain intact. Tertiary structure denaturation involves the disruption of interactions between amino side chains (such as covalent disulfide bridges between cysteine ​​groups, non-covalent dipole-dipole interactions between polar groups, and van der Waals interactions between nonpolar groups in the side chains). Secondary structure denaturation means that the protein loses all regular repeating patterns (e.g., α-helical structures and β-sheets) and adopts a random coil conformation.

[0042] Differential scanning calorimetry (DSC) is known to detect keratin denaturation in hair. DSC is a thermal analysis technique used to measure the transition temperature and heat of conversion (enthalpy) of endothermic and exothermic reactions. DSC is commonly used to measure the melting and solidification temperatures at different melting or cooling rates. DSC is sensitive enough to provide information about the molecular weight distribution of polymers.

[0043] As described above, denaturation measurements were performed on raw hair (control), hair treated with a mixture of ammonium hydroxide and 40% oxidant developer (control), and hair treated with various alkalizing compounds (including 40% oxidant developer). For comparative purposes, hair samples treated with NaOH were also included. NaOH is a very potent alkalizing agent at concentrations above a certain level, inducing significant damage in human hair. NaOH was included as an indicator of the worst level of damage.

[0044] Measurements were performed using either a Mettler Toledo DSC822e (from Mettler Toledo LLC, Columbus OH) or a Discovery DSC 2500 (from TA Instruments, New Castle, DE). Experiments were conducted under nitrogen protection at a scan rate of 5 °C / min over a temperature range of 25 °C to 180 °C. DSC samples were prepared by shredding hair bundles (0.1 to 1.0 mm in size) and weighing them. Hair samples were mixed with deionized water and then sealed in a large-capacity dish for at least 6 hours prior to measurement. The phase transition temperature (keratin denaturation temperature) of each hair sample was analyzed using STARe software (Mettler Toledo DSC822e) or TRIOS software (Discovery DSC 2500). Each hair sample was analyzed at least twice, and the average temperature was used for data analysis. Higher denaturation temperatures indicate less damage to the hair due to treatment with a mixture of alkalizing agent composition and oxidizing agent developer. Results are given in Tables 4A and 4B.

[0045] The above results can be explained by structural, intramolecular hydrogen bonding, and amine group shielding. Table 4B lists thirteen alkanolamine alkalizing agents in order of lowest to highest denaturation temperature. The characteristics that can explain the results, in order of importance, are: the order of the amines (primary, secondary, tertiary); the number of OH groups; the carbon atom distance between the OH groups and the amine; and whether the nitrogen is side-mounted with OH and methyl groups.

[0046] The results also indicate that AP (3-amino-1-propanol) is the only alkalizing agent that produces significantly more damage than any of the common alternatives to ammonium hydroxide—MEA and AMP. Notably, MEA and AMP cause approximately three times the damage of ammonium hydroxide. Serine and DMAP perform closest to ammonium hydroxide, making them suitable as alternatives to all, most, or some of the denaturation temperature of hair.

[0047] All hair samples treated with the primary amine basifying agent compositions (except Tris) showed lower denaturation temperatures than those treated with the ammonium hydroxide compositions, although hair samples treated with serine showed only slightly lower denaturation temperatures. However, among the primary amine basifying agents, AMPD, AEPD, isoserine, and serine all performed significantly better than MEA and AMP, and can therefore be considered suitable for softening and swelling the hair cuticle, and for enabling the reagents and hair-beneficial active ingredients to penetrate into the cortex.

[0048] Among primary amine alkalizing agents, those with two OH groups perform better than those with only one OH group. Within each of these subclasses, those with one or more OH groups that are on average closer to the amine perform better. Here, the term "closer" refers to a smaller number of intercalary carbon atoms. It is also worth noting whether the amine has two or more OH groups "side-attached" within two carbon atoms. The amines in isoserine and DMAPD have two OH groups side-attached, but only one OH group within two carbon atoms.

[0049] All tertiary and secondary amine alkalizing agent compositions (TEA, DMAPD, DEA, DMAMP, and DMAP) caused less damage to hair than ammonium hydroxide compositions. Tris (a primary amine alkalizing agent) also performed well. Among all these alkalizing agents, those with two or three OH groups performed better than those with only one OH group. Among secondary and tertiary amine alkalizing agents, those with more OH groups performed better. Tris is an exception. As a primary amine, Tris is expected to perform poorly. However, the presence of three OH groups within both carbon atoms of the amine, and partial side bonding, appears to contribute to its performance. TEA caused minimal damage to the tested hair samples but can form a residual coating on the hair surface. It can be summarized that primary alkanolamines with at least two OH groups, as well as secondary and tertiary alkanolamines, are preferred when the aim is to limit damage to the hair.

[0050] It appears that at least part of the performance of each alkalizing agent can be attributed to the stabilization or shielding of the amine group caused by intramolecular hydrogen bonds (especially the hydrogen bond between the hydrogen and nitrogen of the hydroxyl group), although some other hydrogen bonds or other effects may also occur. In fact, the only difference between AP (which performed the worst in the DSC test) and DMAP (which performed better than ammonia) is the two methyl groups on the amine of DMAP, which show a significant degree of stabilization of the amine.

[0051] Color enhancement As described herein, spectrophotometry was used to evaluate color and appearance changes in various hair samples resulting from exposure to a variety of alkalizing agent compounds and combinations thereof. Spectrophotometry can be used to measure light reflected from a given surface or object. Data were collected using a Konica Minolta® CM-600d spectrophotometer and the accompanying SpectraMagic NX software to evaluate hair strand color. The standard is to express color as three distinct numerical values ​​(L*, a*, and b*). These values ​​are intended to simulate human eye perception. The a* values ​​representing red / green and the b* values ​​representing yellow / blue of the hair samples are not reported here. However, the L* value represents the light / dark intensity of the measured surface. L* values ​​range from 0 to 100, where 0 is pure black and 100 is pure white. A higher L* value indicates a lighter hair color and a more effective alkalizing agent in enhancing the natural hair color. As described above, L* was measured on raw hair (control), hair treated with a mixture of ammonium hydroxide and 40% oxidant developer (control), and hair treated with various alkalizing compounds (including 40% oxidant developer). For comparative purposes, hair samples treated with NaOH were also included; NaOH is a very potent alkalizing agent at concentrations above a certain level and is expected to induce significant melanin loss. Samples were formed by tying one end of each hair bundle together, with the hair evenly distributed along the bundle. The L* measurements are given in Table 5.

[0052] The results showed that isoserine / oxidant mixtures and 3-amino-1-propanol (AP) / oxidant mixtures were better than ammonium hydroxide / oxidant mixtures (and even similar to or better than NaOH) in enhancing natural color. Furthermore, isoserine showed roughly the same effectiveness as MEA, and significantly better effectiveness compared to AMP, two common alternatives to ammonium hydroxide. 3-Amino-1-propanol (AP) was superior to all of these. Other compositions were less effective than ammonium hydroxide, MEA, and AMP in enhancing color. However, AMPD was almost as good as MEA and ammonium hydroxide. Serine and DMAP, which performed well in terms of damage compared to ammonium hydroxide, were significantly less effective in color enhancement than ammonium hydroxide. This suggests that combinations of alkalizing agents, such as ammonia, MEA, or isoserine combined with serine or DMAP, can achieve the benefits of both.

[0053] The color enhancement results are roughly the opposite of the DSC results above, as all primary amine basifying agent compositions outperformed tertiary amine basifying agent compositions, except for Tris, which performed as well as the tertiary amine basifying agent DMAP. Furthermore, the primary amine basifying agent AEPD did not perform as well as the secondary amine basifying agent DEA, but was close.

[0054] Test combination of alkalizing agents We hypothesize that combinations of alkalizing agents may mitigate their drawbacks while combining the benefits of each. 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 combinations in the first group all involve NH3, as follows: AMPD-NH3, AEPD-NH3, DMAMP-NH3, Tris-NH3, and serinel-NH3. These combinations were tested at different molar ratios as shown in Tables 6-10 below.

[0055] Adding AMPD, AEPD, or serine to NH3 lowers the denaturation temperature, but only slightly. Adding DMAMP or Tris to NH3 raises the denaturation temperature. Almost any amount of Tris results in less damage than AMPD, AEPD, or serine alone, and less damage than AMPD, AEPD, or serine in combination with NH3. In those combinations involving NH3, the L* value decreases to some extent, indicating lower enhancement efficiency than with 100% NH3. Tris tends to reduce the effectiveness of color enhancement.

[0056] The denaturation temperature of each alkalizing agent mixture generally changes linearly with the relative concentration of each alkalizing agent. The combination of DMAMP-NH3 is an exception. In this case, two data clusters exist (see figure). The first cluster of temperature data exists between approximately 0 and 15 molar percentages of DMAMP. The second cluster exists between approximately 25 and 100 molar percentages of DMAMP. DMAMP-NH3 exhibits a significant increase in denaturation temperature from 100% NH3 to 0.5:99.5 (1:199 DMAMP:NH3). This result was unexpected. This nonlinear relationship indicates the range of molar percentage increases in color enhancement with almost no additional denaturation. Therefore, we reasonably expect favorable results 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 the damage is significantly less compared to 100% NH3. Molar ratios of 1:99 to 1:2.5 are preferred; 1:45 to 1:4 are more preferred; and 1:20 to 1:3 are even more preferred.

[0057] In summary, the data above indicate that there are preferred ranges for the relative concentrations of each alkalizing agent combination, depending on the desired effect. A summary of the DSC results is shown in Table 14. Preferred ranges for the molar ratios of each alkalizing agent combination are also shown, based on individual DSC results and results based on both DSC and L* values.

[0058] Cytotoxicity The effects of alkalizing agent compositions on outer root sheath cells and keratinocytes were evaluated. The MultiTox-FluorMultiplex Cytotoxicity Assay (Promega Corp., Madison, WI) simultaneously measured the activities of two proteases: one a marker of cell viability and the other a marker of cytotoxicity. In the assay, the responses of outer root sheath cells and keratinocytes to various concentrations of alkalizing agent, as well as the IC50, were measured. 50 —The concentration that elicits a moderate to high response (the midpoint between baseline and maximum response). In this study, a larger IC50 value was observed. 50 The values ​​indicate that the alkalizing agent had a relatively small effect on cell-induced stress. The results are shown in Table 15.

[0059] For any cell type, the conventional ammonia alternatives MEA and AMP are more cytotoxic than ammonium hydroxide. DMAMP is also more toxic than ammonium hydroxide, but less toxic than the conventional alternative AMP, and less toxic to keratinocytes than MEA. Furthermore, for any cell type, AMPD, AEPPD, DMAPD, and isoserine are significantly less toxic than ammonium hydroxide.

[0060] Tensile strength The effect of the alkalizing agent composition on the tensile strength of hair fibers was measured. Hair bundles were treated with the compositions shown in Tables 2 and 3 as described above. Multiple individual hair fibers were prepared from each bundle for tensile analysis, and the hair was combed and curled using a brass crimp and a Diastron AAS 1600 (Diastron Ltd, UK). The average cross-sectional area of ​​each fiber was measured using a laser micrometer FDS 770 device (Diastron Ltd, UK) at 24°C and 55% relative humidity (RH). All hair fibers were stretched until breakage using a Diastron MTT 686 instrument with a control unit UV1000 (Diastron Ltd, UK). The final results were calculated using software analysis (UvWin 2.35.0000, Diastron, Ltd, UK). The average applied breaking stress is shown in Table 16. A larger breaking stress indicates that the hair fibers were less weakened by the applied alkalizing agent composition.

[0061] The tensile data in Table 16 show the average breaking stress of hair fibers after treatment with the alkalizing composition and oxidizing agent. The samples were compared to NH3 as a baseline. The breaking stress data indicate a general trend of decreasing damage from primary to tertiary amines. For example, tertiary amines (DMAMP, DMAP, DMAPD, TEA) caused similar or less damage to their primary amine analogs (AMP, AP, AMPD, MEA). Furthermore, the transition from primary to secondary to tertiary amines reduced the amount of damage observed with MEA, DEA, and TEA. Additionally, the data show that the position and number of hydroxyl groups affect tensile strength, as seen when comparing AP with AMP with AMPD. The introduction of two hydroxyl groups (AMPD) surprisingly resulted in less damage to the hair fibers. A similar effect was observed with Tris (a primary amine with three side hydroxyl groups). Both examples demonstrate fiber damage similar to that of NH3, with comparable improvements.

[0062] Odor assessment Several alkalizing agent compositions shown in Tables 1 and 2 were graded by professional perfumers. Base formulations without alkalizing agents (Table 1) served as a control. In the primary alkanolamine compositions, the order from no odor to strongest odor was: Control > AMPD = Serine > Tris > MEA = AMP > AEPD > NH3 In tertiary alkanolamine compositions, the order from no odor to strongest odor is as follows: Control > DMAMP > DMAPD > NH3 All evaluated alkanolamine compositions exhibited less odor than the ammonium hydroxide compositions. Among primary amines, AMPD, serinel, and Tris performed better than MEA and AMP (two conventional ammonia substitutes). The two tertiary amines tested performed worse than MEA and AMP. Example

[0063] In summary, six of the eleven alkanolamines performed well in DSC analysis, indicating reduced hair fiber damage compared to ammonium hydroxide. Eight of the eleven alkanolamines performed comparable to NH3 in tensile tests. In DSC analysis, ten of the eleven alkanolamines showed reduced hair fiber damage compared to MEA and AMP (common alternatives to ammonium hydroxide) when used as alkalizing agents in hair colorants. In tensile strength analysis, eight of the eleven alkanolamines showed reduced hair fiber damage compared to MEA and AMP when used as alkalizing agents in hair colorants. Three alkanolamines were superior to ammonium hydroxide in enhancing hair color. One of these (isoserine) was significantly superior to AMP in enhancing hair color and roughly the same as MEA. Furthermore, combinations of the eleven alkalizing agents, with or without ammonium hydroxide, have been shown to be beneficial in reducing hair damage, improving color enhancement, or both. We have found that for mixtures of two alkalizing agents, the keratin denaturation temperature varies approximately linearly with the relative concentration of each alkalizing agent, except in the case of DMAMP-NH3. This result was unexpected. Combined with L* value measurements, this indicates that there are preferred ranges of relative concentrations for each combination of alkalizing agents, and we have determined these.

[0064] Primary alkanolamines have a better odor than tertiary alkanolamines. For outer root sheath cells and keratinizing cells, MEA, AMP, and DMAMP are more cytotoxic than ammonium hydroxide. However, for either cell type, AMPD, AEPD, DMAPD, and isoserine are significantly less toxic than ammonium hydroxide. Some or all of these properties are beneficial in both oxidative and non-oxidative hair treatments.

[0065] Generally, we have demonstrated the suitability of various alkanolamines for softening and swelling the hair cuticle, enabling agents and hair-beneficial active ingredients to penetrate the cortex. These results can be applied to various types of hair treatment applications, but we have specifically demonstrated their effectiveness in hair coloring treatments. We have shown that, depending on the type of hair coloring application, the use of ammonium hydroxide can be reduced or eliminated.

[0066] discuss Based on observations, it can be inferred that intramolecular hydrogen bonds within alkanolamines lead to conformations that provide a certain degree of amine stabilization. Of particular interest are the hydrogen bonds between the nitrogen atom and one or more hydroxyl groups of the alkanolamine. This type of intramolecular bonding provides an explanation for the changes we have observed in hair fiber degeneration and color enhancement. Generally, the more hydrogen bonds involved in the amine, the less damage the hair suffers, but at the cost of less effective color enhancement. However, those alkanolamine molecules in which the electron bond donor is located at just two carbons away from the nitrogen atom are of particular interest. Primary alkanolamines with two or more hydroxyl groups at the C2 position are useful alkalizing agents in hair treatment products. Moreover, secondary and tertiary alkanolamines with at least one hydroxyl group at the C2 position are also useful.

[0067] While specific embodiments of the invention have been described and illustrated, it will be apparent 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. Therefore, it is intended that all such changes and modifications be covered within the scope of the invention in the appended claims.

Claims

1. An alkalizing agent composition comprising: One or more major intermediates and / or coupling agents, ammonia and serine alcohol, wherein the molar ratio of serine alcohol to ammonia is 1:2.5 to 1:

9.

2. An alkalizing agent composition comprising one or more major intermediates and / or coupling agents, and serine alcohol.

3. A hair dyeing product, comprising a first container and a second container, wherein: The first container contains an alkalizing agent composition comprising one or more major intermediates and / or coupling agents, and serinel; and The second container contains an oxidizing agent composition.

4. The hair dye product according to claim 3, wherein the product has a pH of 8 to 12.

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