Hair treatment composition comprising oil containing olefinic unsaturated hydrocarbon

Abstract

The present invention provides a hair and fiber treatment composition, which provides a smooth feeling to the hair and fibers continuously by supplying a transition metal as a catalyst to a thiol residue formed when the hair or fibers are damaged during a chemical or physical care process, so as to rapidly and massively bind an olefinic unsaturated hydrocarbon through a thiol-ene reaction.

Description

Technical Field

[0001] This application claims the benefit of priority based on Korean Application No. 10-2019-0146448 filed on November 15, 2019 and Korean Application No. 10-2019-0146449 filed on November 15, 2019, and all contents disclosed in the specifications and drawings of the related applications are incorporated herein by reference.

[0002] The present invention relates to a hair treatment composition comprising an oil containing an olefinically unsaturated hydrocarbon. Background Art

[0003] Hair cosmetics generally have the function of washing hair to remove dirt from the scalp and hair and keep the hair clean and beautiful, and are also used for additional purposes such as making combing easier, giving hair a soft, smooth or moist feeling, reducing friction on the hair surface, preventing static electricity or protecting hair. Recently, the demand for hair dyes, bleaching agents or perming agents that change the color or shape of hair for beauty purposes is increasing.

[0004] Hair dyes open and close the stratum corneum by adjusting pH, allowing the dyeing ingredients to penetrate into the cortex, thereby changing the color of the hair. In this process, the disulfide of the protein is destroyed to form cysteic acid or cysteine. Even if it is repaired to acidity, the remaining part is more than 20% to 30%, which will cause damage to the hair, such as reducing the smoothness.

[0005] As a study to overcome this problem, there have been methods of suppressing the formation of cysteine ​​by introducing specific molecules in the form of amides (EP 2417964 A1), or applying oil to provide a smooth feeling without significantly affecting the oxidative power. However, these methods have the disadvantages of reducing the beauty function as a conventional purpose, or causing a sticky feeling during use due to temporary application, thereby reducing satisfaction due to unpleasantness.

[0006] Many documents are referenced throughout this specification, and their citations are marked. The disclosures of the cited documents are incorporated into this specification by reference in their entirety, so as to more clearly illustrate the level of the technical field to which the present invention belongs and the content of the present invention. Summary of the invention

[0007] Technical issues

[0008] The present invention relates to a hair treatment composition which contains a metal catalyst or an oxidation initiator to activate a thiol-ene reaction to protect and repair oxidized hair, thereby increasing a high conditioning effect.

[0009] Therefore, the object of the present invention is to rapidly and massively bind an oil containing olefinic unsaturated hydrocarbons to thiol residues formed when hair or fibers are damaged during chemical or physical care through a thiol-ene reaction, thereby providing a smooth feeling to the hair continuously.

[0010] Another object of the present invention is to provide a hair or protein fiber treating composition having the above functions.

[0011] Another object of the present invention is to provide a hair treatment composition, particularly a hair dye composition, having the above functions.

[0012] Another object of the present invention is to provide a hair product and a fiber treatment product having the above functions.

[0013] More specifically, an object of the present invention is to provide the following specific examples.

[0014] Specific example A1. A hair treatment composition comprising a transition metal catalyst and an oil containing an olefinic unsaturated hydrocarbon.

[0015] Specific example A2. The hair treatment composition according to Specific example A1, wherein the polymer has an effect of protecting hair, repairing hair, imparting a conditioned feel, or preventing hair oxidation.

[0016] Specific example A3. The hair treatment composition according to any one of the above specific examples, characterized in that the above transition metal catalyst is one or more selected from the group consisting of monovalent transition metals, divalent transition metals and salts thereof.

[0017] Specific example A4. The hair treatment composition according to any one of the above specific examples, characterized in that the transition metal catalyst is one or more selected from the group consisting of copper salts and iron salts.

[0018] Specific example A5. The hair treatment composition according to any one of the above specific examples, characterized in that the above-mentioned olefinic unsaturated hydrocarbon is a C6-C22 fatty acid containing at least one unsaturated group.

[0019] Specific example A6. The hair treatment composition according to any one of the above specific examples, characterized in that the transition metal catalyst promotes the thiol-ene reaction between cysteine ​​present in the hair and the oil containing the olefinic unsaturated hydrocarbon.

[0020] Specific example A7. A hair product comprising the hair treatment composition according to any one of the above specific examples.

[0021] Specific example A8. The hair product according to specific example A7 is characterized in that the above-mentioned hair product is selected from the group consisting of a bleaching agent, a dyeing agent, a perming agent, a hair repair agent, a hair treatment agent, a hair nutrient agent, a hair care agent, a hair cleanser, a shampoo, a conditioner, a hair nourishing agent, a hair conditioner, a hair lotion, a hair gel, a hair mask, a hair cream, a hair essence, a hair powder, a hair spray, a hair oil, a hair fixative, a patch, a spray and a dyeing post-treatment agent.

[0022] Specific example A9. A protein-based fiber treatment composition comprising a transition metal catalyst and an oil containing an olefinic unsaturated hydrocarbon.

[0023] Specific example A10. The composition for treating protein-based fibers according to specific example A9 is characterized in that the transition metal catalyst promotes the thiol-ene reaction between cysteine ​​present in the protein-based fibers and the oil containing olefinic unsaturated hydrocarbons.

[0024] Specific example B1. A hair treatment composition comprising (i) an oxidation initiator and (ii) an oil containing an olefinic unsaturated hydrocarbon.

[0025] Specific example B2. The hair treatment composition according to specific example B1, further comprising an oxidation dye.

[0026] Specific example B3. A hair treatment composition according to any one of the above specific examples, characterized in that the above-mentioned oxidation dye is one or more selected from the group consisting of phenylenediamine, aminophenol, resorcinol, aminocresol, methylhydroxyethylaminophenol, nitrobenzenediamine and toluenediamine sulfate.

[0027] Specific example B4. The hair treatment composition according to any one of the above specific examples, characterized in that the above-mentioned oxidation initiator is one or more selected from the group consisting of hydrogen peroxide, sodium perborate, sodium percarbonate, ammonium persulfate, bismaleimidoethoxyethane, calcium peroxide, ferric chloride, hypochlorous acid, laccase, magnesium peroxide, MEK (methyl ethyl ketone) peroxide, melanin peroxide, ozonized turpentine, phthalimidoperoxycaproic acid, potassium bromate, potassium kaluate, potassium chlorate, potassium monopersulfate, potassium persulfate, PVP-hydrogen peroxide, sodium bromate, sodium carbonate peroxide, sodium iodate, sodium perborate, sodium persulfate, strontium peroxide, urea peroxide and zinc peroxide.

[0028] Specific example B5. The hair treatment composition according to any one of the above specific examples, characterized in that the above-mentioned olefinic unsaturated hydrocarbon is an unsaturated fatty acid.

[0029] Specific example B6. The hair treatment composition according to any one of the above specific examples, characterized in that the above-mentioned oil containing olefinic unsaturated hydrocarbons contains 50% by weight or more of unsaturated fatty acids.

[0030] Specific example B7. A hair treatment composition according to any one of the above specific examples, characterized in that the above-mentioned oil containing olefinic unsaturated hydrocarbons is one or more selected from the group consisting of olive oil, macadamia oil, jojoba oil, meadowfoam oil, argan oil, camellia oil, grape seed oil, sunflower oil, avocado oil, canola oil, corn oil, cottonseed oil, hemp seed oil, flax seed oil, linseed oil, palm oil, peanut oil, safflower oil and soybean oil.

[0031] Specific example B8. A hair treatment composition according to any one of the above specific examples, characterized in that

[0032] The above oxidation dye is in the first agent,

[0033] The above oxidation initiator is in the second agent,

[0034] The above-mentioned oil containing olefinic unsaturated hydrocarbons is separately contained in the third agent.

[0035] Specific example B9. The hair treatment composition according to any one of the above specific examples, characterized in that the first agent, the second agent and the third agent are mixed and applied to the hair immediately before use.

[0036] Specific example B10. The hair treatment composition according to any one of the above specific examples, characterized in that the above oxidation initiator promotes the thiol-ene reaction between cysteic acid present in the hair and the above olefinic unsaturated hydrocarbon.

[0037] Specific example B11. A hair treatment composition according to any one of the above specific examples, characterized in that the above hair treatment composition has one or more effects selected from the group consisting of hair protection, hair repair, conditioning, hair oxidation prevention, dyeing damage prevention and color durability effect.

[0038] Specific Example C1. Use of the composition according to any one of the above specific examples for protecting hair, repairing hair, giving hair a conditioned feel, preventing hair oxidation, preventing hair dyeing damage and / or maintaining hair color.

[0039] Specific example C2. A method for protecting hair, repairing hair, imparting a conditioning feel to hair, preventing hair oxidation, preventing hair dyeing damage and / or maintaining hair color, comprising applying the composition described in any one of the above specific examples to a subject.

[0040] Specific Example C3. Use of the composition according to any one of the above specific examples in the preparation of a hair product for protecting hair, repairing hair, giving hair a conditioned feel, preventing hair oxidation, preventing hair dyeing damage and / or maintaining hair color.

[0041] Technical Solution

[0042] The technology of the present invention is to supply an oil containing olefinic unsaturated hydrocarbons to damaged hair or protein fibers to cause a thiol-ene reaction between the thiol group of cysteine ​​present in the damaged hair or protein fibers and the unsaturated group, thereby repairing the damage and increasing the smoothness and moisturizing conditioning feeling. As described above, the reaction of attaching a lipid component to cysteine ​​to improve the hair and protein fibers can be promoted using a metal catalyst and / or an oxidation initiator.

[0043] I. Hair treatment composition using a metal catalyst

[0044] One aspect of the present invention is to provide a hair treatment composition comprising a transition metal catalyst and an oil containing an olefinic unsaturated hydrocarbon.

[0045] Transition metal catalysts, in particular, combine with lipids to form insoluble salts, providing so-called scale, thereby causing a side effect of increasing the stiffness of hair, and therefore are prohibited from being added to hair cosmetics. However, in the present technology, transition metal ions are responsible for donating electrons as free radicals for thiol-ene reactions, and olefins combined with hair cysteine ​​provide a large amount of long-lasting smoothness, so the metal catalyst instead produces an effect of increasing the smoothness.

[0046] As one embodiment of the present invention for solving the above-mentioned problems, the present invention provides a bond having the following Chemical Formula 1.

[0047] [Chemical formula 1]

[0048] AZR'

[0049] In Chemical Formula 1, Z is an unsaturated bond linking group, A is a functional group capable of forming a covalent bond on hair, wherein, in Z that activates a thiol-ene reaction by binding an olefin linking group to damaged hair, R' is a C1-22 alkyl group, or an ionizable functional group.

[0050]

[0051] As mentioned above, M, as a transition metal, acts as a catalyst in the thiol-ene reaction.

[0052] Cysteine ​​gives the hair a rough conditioning feel and reduces moisture, significantly increasing the hair's sense of damage. If the oil is penetrated into the hair or adsorbed to the outside, the conditioning of the hair can be increased, but it is removed during washing and rinsing, so there is a limitation that it only provides a temporary effect.

[0053] The above-mentioned transition metal catalyst can be monovalent copper (I) iodide (Cu(I) iodie), copper (I) oxide (Cu(I) chloride), copper (I) bromide (Cu(I) bromide), copper (I) cyanide (Copper (I) cyanide), copper (I) acetate (Copper (I) acetate), copper (II) oxide (Copper (II) chloride (Copper (II) chloride), copper (II) sulfate (CuSO4) and the like. The divalent copper(II) acetate may be copper(II) acetate, copper(II) bromide, copper(II) trifluoromethanesulfonate, copper(II) fluoride, copper(II) sulfide, copper(II) acetylacetonate, copper(II) acetate monohydrate, copper(II) nitrate trihydrate, copper(II) phthalocyanine, copper(II) hydroxide, copper(II) carbonate basic, copper(II) 2-ethylhexanoate, copper(II) hexafluoroacetylacetonate hydrate, or the like.The iron(III) oxide may be trivalent iron(III) oxide, iron(III) citrate, iron(III) chloride, iron(III) acetylacetonate, iron(III) oxide, iron(III) nitrate nonahydrate, iron(III) tartrate, iron(III) sulfate hydrate, iron(III) trifluoromethanesulfonate, iron(III) pyrophosphate, iron(III) ferrocyanide, iron(III) bromide, iron(III) perchlorate hydrate, iron(III) ionophore IV, or iron(III) ionophore IV. The invention also includes, but is not limited to, iron (III) phosphate dehydrate, iron (III) oxalate hexahydrate, iron (III) citrate tribasic monohydrate, iron (III) p-toluenesulfonate hexahydrate, iron (III) phosphate tetrahydrate, iron (III) fluoride, iron (III) phthalocyanine chloride, iron (III) arsenide, iron (III) nitrate, and iron (III) fluoride trihydrate.

[0054] The composition of the present invention contains an oil containing olefinic unsaturated hydrocarbons for the purpose of providing moisture to hair or moisturizing the hair. The oil may contain, for example, C6 to C22 fatty acids containing one or more unsaturated groups as olefinic unsaturated hydrocarbons. In addition, an oil that can change the conditioning feeling in the hair by adsorption or penetration into the hair can be used without limitation.

[0055] As non-limiting examples of the above-mentioned oils, water-insoluble and non-volatile components collectively referred to as silicones, such as dimethicone, cyclomethicone, amination silicone, trimethylsilyl amodimethicone or vinyl silicone, and their derivatives, vegetable oils such as jojoba oil, vegetable fats, animal oils, animal fats, hydrocarbon oils or synthetic ester oils, etc. can be used. The hydrocarbon oil may include liquid paraffin, isoparaffin or hydrogenated polydecene, and the ester oil may include isopropyl myristate, isopropyl palmitate, isostearyl isostearate or C12-15 alkyl benzoate, triethylhexanoin, squalane, palm oil, olive oil, PPG-3 caprylyl ether, capric / caprylic triglyceride, isostearyl isostearate, coconut oil, polyglyceryl-6 octacaprylate, hydrogenated polydecene, jojoba seed oil, DI-C 12-13 alkyl maleate, but are not limited thereto.

[0056] The oil containing olefinic unsaturated hydrocarbons may preferably contain more than 50% by weight of unsaturated fatty acids. Examples thereof include, but are not limited to, olive oil, macadamia oil, jojoba oil, meadowfoam oil, argan oil, camellia oil, grape seed oil, sunflower oil, avocado oil, canola oil, corn oil, cottonseed oil, hempseed oil, linseed oil, linseed oil, palm oil, peanut oil, safflower oil, and soybean oil.

[0057] In addition, the content of the above oil may be 0.05 to 10 wt %, specifically 0.1 to 6 wt %, but is not limited thereto.

[0058] The composition of the present invention as described above has the effects of protecting hair, repairing hair, imparting conditioning feeling or preventing hair oxidation, and can also be used to protect protein fibers other than hair. In the above fiber treatment composition, the transition metal catalyst functions to promote the thiol-ene reaction between cysteine ​​present in the protein fiber and the above olefinic unsaturated hydrocarbon based on the same principle as described above for the hair treatment composition, thereby imparting the effects of protecting and repairing damage to the protein fiber (e.g., natural fiber derived from an animal, protein regenerated artificial fiber, etc.).

[0059] The hair treatment composition of the present invention may further contain at least one selected from the group consisting of fatty substances commonly used in hair products, organic solvents, solubilizers, thickeners, gelling agents, softeners, antioxidants, suspending agents, stabilizers, foaming agents, fragrances, surfactants, water, ionic or nonionic emulsifiers, fillers, metal ion blocking agents, preservatives, vitamins, blocking agents, humectants, essential oils, dyes, pigments, hydrophilic or lipophilic active agents, etc.

[0060] In addition, the composition of the present invention may further include additives that provide beneficial properties for the human body. For example, it may further include additives that impart beneficial properties to the human body (e.g., cleaning, curling (volume), tidying, protecting, blocking, moisturizing, dyeing, coloring, bleaching, antiperspirant, deodorant, antiseptic, cooling, hair removal, hair growth, dandruff prevention, hair removal prevention, hair care, anti-inflammatory, fragrance, fragrance, whitening, aging prevention, wrinkle improvement, astringent, soothing, contraction, sebum inhibition, keratin exfoliation, sterilization, anti-inflammatory, antipruritic, deodorant, antihistamine, anti-seborrheic, blood circulation promotion, ultraviolet blocking or skin metabolism promotion, etc.).

[0061] In addition, the composition of the present invention may further contain preservatives, thickeners, viscosity modifiers, pH modifiers, fragrances, dyes or conditioning agents that are generally used as components of hair compositions, and they can be easily purchased and used commercially. Examples of preservatives include benzoic acid and salts, methyl paraben, methylchloroisothiazolinone or a mixture of methylisothiazolinone (trade name: Kathon CG, manufacturer: The Dow Chemical Company), etc. As thickeners and viscosity modifiers, hydroxypropyl methylcellulose, hydroxymethylcellulose, sodium chloride, ammonium chloride, propylene glycol, hexylene glycol, sodium xylenesulfonate or ammonium xylenesulfonate, etc. can be used. As pH modifiers, citric acid, sodium hydroxide or triethanolamine, etc. can be used. As dyes, water-soluble tar pigments, etc. can be used. And as conditioning agents, animal and plant extracts, proteins and protein variants, higher fatty acids, etc. can be used.

[0062] The composition of the present invention can be prepared in the form of a general emulsified formulation or a solubilized formulation. In addition, the composition of the present invention can be prepared in any formulation that can be applied to the scalp, such as a liquid, cream, paste or solid.

[0063] In addition, the present invention provides a hair product comprising the above-mentioned hair treatment composition, and the above-mentioned hair product can be selected from the group consisting of a bleaching agent, a dyeing agent, a perming agent, a hair treatment agent, a hair clinic agent, a hair nutrient, a hair conditioning agent, a hair cleanser, a shampoo, a hair conditioner, a hair tonic, a hair conditioner, a hair lotion, a hair gel, a hair mask, a hair cream, a hair essence, a hair powder, a hair spray, a hair oil, a hair fixative and a dyeing post-treatment agent, but is not limited thereto.

[0064] II. Hair treatment composition using an oxidation initiator

[0065] Another aspect of the present invention provides a hair treatment composition comprising (i) an oxidation initiator and (ii) an oil containing an olefinic unsaturated hydrocarbon.

[0066] When using oxidative hair dyes or bleaching agents, the hair protective lipid layer on the surface of the hair is hydrolyzed by 50-70% or more after just one dyeing, which easily causes hair damage and color fading. Previously, a technology has been introduced to temporarily coat the damaged lipid part with silicone, cationic polymers, etc. to improve damage and color durability, but due to simple adsorption or ionic bonding, it lacks durability, which is a situation that needs improvement.

[0067] Therefore, the present invention provides a hair treatment composition which can covalently bond a substitute lipid component to a thiol group generated after hair lipid damage through a thiol-ene reaction, thereby improving the lipid repair and water resistance of damaged hair, thereby improving the problems of hair damage and reduced durability of dyed color caused by oxidative dyeing and bleaching.

[0068] The oxidative initiator contained in the hair treatment composition of the present invention is an initiator that promotes oxidation and bleaching of the dye and initiates covalent bonding between the keratin residues of the hair and the natural oil or its derivative, and includes at least one oxidative and initiator component that promotes the reaction, and for example, refers to a component that promotes the oxidative initiation reaction, such as hydrogen peroxide, sodium perborate, sodium percarbonate, ammonium persulfate, bismaleimidoethoxyethane, calcium peroxide, ferric chloride, hypochlorous acid, laccase, magnesium peroxide, MEK (methyl ethyl ketone) peroxide, melanin peroxide, ozonized turpentine, phthalimidoperoxycaproic acid, potassium bromate, potassium kaluate, potassium chlorate, potassium monopersulfate, potassium persulfate, PVP-hydrogen peroxide, etc. Peroxide), sodium bromate, sodium carbonate peroxide, sodium iodate, sodium perborate, sodium persulfate, strontium peroxide, urea peroxide and zinc peroxide, etc.

[0069] The oil containing olefinic unsaturated hydrocarbon contained in the hair treatment composition of the present invention is the same as described in the above section I. Preferably, the natural oil having an unsaturated double bond group used in the present invention has one or more unsaturated groups such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, gadoleic acid (11-eicosanoic acid), neuraminic acid, and the like, and the unsaturated oil group composition is preferably 50% or more of the entire oil composition.

[0070] As the natural oil containing 50 wt % or more of unsaturated fatty acids and its derivatives, for example, one or more selected from the group consisting of olive oil, macadamia oil, jojoba oil, meadowfoam oil, argan oil, camellia oil, grape seed oil, sunflower oil, avocado oil, canola oil, corn oil, cottonseed oil, hempseed oil, linseed oil, linseed oil, palm oil, peanut oil, safflower oil and soybean oil can be used, but it is not limited thereto.

[0071] The content of the oil component is more preferably 0.5 to 5.0% in the entire hair dye composition, and the content of the oxidation initiator is more preferably 0.1 to 15%.

[0072] The hair treatment composition of the present invention may further contain an oxidation dye. Specific examples thereof include at least one selected from the group consisting of phenylenediamine, aminophenol, resorcinol, aminocresol, methylhydroxyethylaminophenol, nitrophenylenediamine and toluenediamine sulfate. Specifically, p-phenylenediamine, m-phenylenediamine, m-aminophenol, toluene-2,5-diamine sulfate, p-aminophenol, nitro-p-phenylenediamine, p-amino-o-cresol and resorcinol can be used.

[0073] The hair treatment composition of the present invention may be composed of two or more formulations, and the oxidation initiator and the olefinically unsaturated hydrocarbon-containing oil may be contained in different formulations.

[0074] As a preferred specific example of the present invention, the oxidation initiator is contained in the first agent, and the oil containing the olefinic unsaturated hydrocarbon is contained in the second agent separately, and they can be mixed and applied to the hair immediately before use.

[0075] In a preferred embodiment of the present invention, the oxidation dye is contained in the first agent, the oxidation initiator is contained in the second agent, and the oil containing the olefinic unsaturated hydrocarbon is contained in the third agent separately, and they can be mixed and applied to the hair immediately before use.

[0076] As an example, a hair treatment product comprising the first agent, the second agent and the third agent containing the above-mentioned components can be provided. More preferably, the hair treatment product can be a hair dyeing or bleaching product, and more preferably, it can be a hair dyeing product.

[0077] As an example, a hair treatment product consisting of the first agent, the second agent and the third agent containing the above-mentioned components can be provided. More preferably, the hair treatment product can be a hair dyeing or bleaching product, and more preferably, it can be a hair dyeing product.

[0078] The inventors have found that oils with a large number of unsaturated groups lose their unsaturated groups due to hydrolysis under alkaline conditions, and if mixed with hydrogen peroxide, a reaction is initiated due to oxygen free radicals. Therefore, when included in a dosage form, the oil loses its reactivity and cannot be covalently bonded. Therefore, the oil should be mixed and used immediately before using the hair dye.

[0079] The hair treatment composition of the present invention containing the oxidation initiator as described above has one or more effects selected from the group consisting of hair protection, hair repair, imparting a conditioned feel, preventing hair oxidation, preventing dyeing damage, and color durability effects.

[0080] The hair treatment composition of the present invention may contain, in addition to the above-mentioned components, components generally contained in hair dyes and bleaching agents, etc. For example, although not limited thereto, it may contain a metal blocking agent, a solvent, a surfactant, a thickener, and a fragrance.

[0081] The hair treatment composition of the present invention is not limited thereto, but may be used in the form of powder, cream, lotion, gel, foam, aerosol or liquid.

[0082] Effects of the Invention

[0083] The present invention has the effect of semi-permanently bonding olefin oil to cysteine ​​present in damaged hair or protein fibers through a thiol-ene reaction, thereby significantly improving the long-lasting hair protection and conditioning feeling. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] Figure 1 The process of repairing oxidatively damaged hair through a thiol-ene reaction with an olefin-based oil is shown.

[0085] Figure 2 An image showing the degree of damage in a hair cross section. DETAILED DESCRIPTION

[0086] Below, the present invention will be described in more detail by examples. These examples are only used to describe the present invention in more detail, and it is obvious to those skilled in the art that the scope of the present invention is not limited by these examples.

[0087] The materials and reagents used in this experimental example were purchased from cosmetic raw material manufacturers and commercial suppliers and used.

[0088] Experimental example

[0089] I. Hair treatment composition containing a metal catalyst

[0090] 1. Preparation of Decolorizing Agent

[0091] [Table 1]

[0092]

[0093] A decolorizing agent was prepared as shown in Table 1. To two preparations of the decolorizing agent, 4% of an oil containing olefinic unsaturated hydrocarbons and 0.4% (i.e., 10% of the oil containing olefinic unsaturated hydrocarbons) of a metal catalyst were added.

[0094] 1 g of hair bundle was treated with a bleaching agent twice the weight of the hair for 20 minutes (normal bleaching treatment time), and then rinsed with running water at a flow rate of 4 ml / sec for 5 minutes.

[0095] 2. Evaluation of smoothness when adding transition metal catalyst ions

[0096] [Table 2]

[0097]

[0098] As shown in Table 2, Cu and Fe were used and selected as transition metal catalysts included in the two agents of Table 1. As described in the above examples, transition metal catalysts exist in many types according to counterions, but in order to compare the effects of metal catalysts under the same conditions of chemical binding force, bromide, chloride and iodide were selected restrictively. Since there is no trivalent Cu compound, the counterion for Cu in the monovalent and divalent experiments has the same element and Fe was used for the experiment.

[0099] However, as shown in Table 3, the iodide of Example I-2 and the chloride of Example I-3 showed similar results in the monovalent ion experiment, so the counter ion compounds of iodide were excluded from the divalent and trivalent samples in this experiment.

[0100] Comparative Example I-1 is damaged hair, and Comparative Example I-2 is hair containing olefin. In Comparative Example I-2, olefin was applied in an amount twice the weight of the hair, and then washed for 5 minutes.

[0101] The smoothness of the experimental samples was evaluated by friction using MTT 175 Miniature Tensile Tester (DiaSTRON, GB). The hair treated as above was rinsed for several minutes, then dried with a hair dryer for 2 minutes, and kept at 25° C. for one day in a constant temperature and humidity chamber with a humidity of 50% to make the moisture inside the hair constant, and then the friction was measured in the same constant temperature and humidity chamber. The results are shown in Table 3 below.

[0102] At this time, the hair bundle was washed with anionic surfactant sodium lauryl sulfate, and then this was used as a reference value, and the difference value with the relevant measured value was compared to calculate the change value (%) of the friction force on the hair surface, as shown in Table 3. The larger the value, the greater the change value of the friction force, which reflects the increase in smoothness.

[0103] [Table 3]

[0104]

[0105] From the results in Table 3, it can be seen that when modified to monovalent or divalent, the frictional force, which is inversely proportional to the smoothness, changes significantly and decreases. On the other hand, it can be seen that Fe significantly reduces the frictional force in divalent as in Example 1-7, but as shown in Comparative Examples 1-3 and 1-4, when a trivalent metal catalyst acts, the group bound to the fatty acid acts more on the hair, so there is no effect on the reduction of frictional force. This is because the activation energy of the trivalent radical ion as a catalyst acting on thiol-ene is high, so it does not affect the hair cysteine. In addition, it can be seen that due to the metallic feel peculiar to Fe, the surface is rougher than that of Comparative Example 1-2 which does not contain a metal catalyst.

[0106] On the other hand, it can be seen from Example 1-4 that even if the same metal ion is a divalent ion, there are differences in the effect of preventing surface damage according to the counter ion. This is because when the counter ion is a hexavalent sulfate, the charge density is relatively low, so it is impossible to promote the thiol-ene free radical reaction. The Br or Cl series with relatively high charge density fully undergoes free radical reactions, so it can be considered to be the most suitable as a metal catalyst.

[0107] Comparative Example I-2 showed similar friction to Example I-4, so it can be considered that a metal catalyst is not necessarily required. However, this is a temporary effect rather than a semi-permanent effect. The oily feeling immediately after the oil is applied has a conditioning effect, but since there is no bond with the hair, the oil is completely washed off when washed, and the final value is the same as that of Comparative Example I-1. In order to obtain a high friction change value by olefin treatment alone, it was confirmed that an excess of olefin treatment of more than 2 times the weight of the hair was required, and this was removed by repeated washing, so it was only a temporary effect.

[0108] Finally, the present metal catalyst was selected as the Cu(II) chloride with the best smoothness conditioning effect and the content was changed. It was confirmed that the best effect was found when the content was 1% to 15% compared with olefin.

[0109] 3. Preparation of pretreatment agent and effect evaluation

[0110] In the above-mentioned process of bleaching hair, a metal catalyst is added and treated on the hair. As shown in Table 4 below, before bleaching, that is, before treating the bleaching agent, a bleaching pretreatment agent for treating the hair with a metal catalyst is prepared separately to observe when the metal catalyst treatment is effective.

[0111] [Table 4]

[0112]

[0113] The metal catalyst contained in the above pretreatment agent used those shown in the following Table 5. As described above, pretreatment agents 1 to 8 containing both the metal catalyst and double bond group olive oil were prepared, and the smoothness was evaluated by the change of the friction force on the hair surface according to the one-time use of these before using the bleaching agent as a peroxide series hair cosmetic. The results are shown in the following Table 5.

[0114] [Table 5]

[0115]

[0116] As can be seen from Table 5, if the metal catalyst and the double bond group are pretreated together before using the bleaching agent as a peroxide series hair cosmetic, there is no effect on enhancing the thiol-ene reaction. When olive oil or oil is adsorbed alone, it penetrates due to the hydrophobic combination with the protein inside the hair, as studied in the literature [Ruetsch, SB; Kamath, YK; Rele, AS; Mohile, RB, Secondary ion mass spectrometric investigation of penetration of coconut and mineral oils into human hair fibers: Relevance to hair damage. Journal of Cosmetic Science 2001, 52 (3), 169-184.]. This induces separation from the metal catalyst, so the pretreatment seems to have no effect. Therefore, it can be seen that the metal catalyst is used together with the oxidant, and when the disulfide of the hair is damaged, the thiol-ene reaction must be immediately carried out.

[0117] 4. Evaluation of the effect of using alkaline earth metal catalysts

[0118] As the metal catalyst contained in the two agents in Table 1 above, the alkaline earth metal catalysts described in Table 6 below were used, and the effects were evaluated. A thiol-ene reaction was caused by one use of the bleaching agent containing the alkaline earth metal catalyst, and the reaction degree was evaluated as a change rate (%) of friction force on the hair surface, which is shown in Table 6 below.

[0119] [Table 6]

[0120]

[0121] As a result of the experiment, when an alkaline earth metal was used as a metal catalyst, there was no reaction at all, as shown in the above Table 6. This is because, in the case of alkaline earth metals, electrons are filled into s or f orbitals and thus radical reactions are difficult, whereas in the case of Cu or Fe, electrons are filled into d orbitals and thus radical reactions are easy to proceed, and this promotes thiol-ene reactions as metal catalysts.

[0122] 5. Evaluation of glossiness, bending strength and combing strength

[0123] In Table 7, the gloss was measured by L=100*Sin / S_out*1 / W_visual using a colorimeter Samba (Bossa Nova Vision, Fr), S is the amount of reflection, and W is the width (angle) of the measurement range.

[0124] In Table 7, in order to evaluate the strength (rigidity) of the hair, the evaluation was performed using a bending strength evaluator KES-FB2-S (KATOTECH, Japan).

[0125] In Table 7, for combing strength, the friction force consumed in the combing test was evaluated using an MTT 175 micro tensile tester (DiaSTRONG, GB). If the value becomes larger, it means that the force consumed in combing becomes larger, thus indicating that the hair is tangled.

[0126] The examples and comparative examples in Table 7 are shown in Table 5, and the physical property values ​​of the hair treated with the metal catalyst in the pretreatment agent are indicated. Comparative Example I-5 is untreated, and Comparative Example I-6 contains only olefin. Examples I-8 and I-9 are treated with a pretreatment agent containing olefin together with Cu(I) chloride and Cu(II) chloride, and Comparative Example I-7 is the physical property value of the hair treated with a pretreatment agent containing Fe(III) chloride.

[0127] [Table 7]

[0128]

[0129] It can be seen in Examples 7 and 8 that while the moisturizing value increases, the bending strength value increases and the combing strength value decreases. As can be seen in the above instrumental evaluation, it is confirmed that the monovalent and divalent metal catalyst radicals added in the present invention complete the thiol bonding of olefins through the catalytic reaction, thereby significantly increasing the conditioning feeling.

[0130] 6. Evaluation of the degree of damage to the hair when used in hair dyes

[0131] Finally, in order to evaluate the degree of damage to the inside of the hair when used in hair dyes, hair cross-section samples were prepared based on the literature [Ryu, SR; Jang, W.; Yu, SI; Lee, BH; Kwon, OS; Shin, K., FT-IR Microspectroscopic Imaging of Cross-Sectioned Human Hair during a Bleaching Process. J. Cosmet. Dermatol. Sci. Appl. 2016, 6(5), 181-190.] and the hair was scanned at 1072 cm -1 Cystein monoxide generated when hair damage occurs is measured and IR mapping is performed. Amide I is captured as a reference point for normalization. As a result, the obtained hair cross-section damage degree image is shown in Figure 2 .

[0132] exist Figure 2 The wave number is 1072cm -1 The color intensity (green: high, blue: low) indicates the degree of damage. Only the result image #1 is untreated hair, and from #2 onwards, oxidative damage is applied with hair dye. The circles in the image refer to the cross-section of the hair.

[0133] from Figure 2 It can be seen from the results that, as shown in #5, when divalent copper ions are used as chloride counter ions, damage inside the hair is greatly prevented during hair dyeing and bleaching or perming oxidative damage.

[0134] II. Hair Treatment Compositions Containing Oxidative Initiators

[0135] 1. When the oil is directly mixed and applied to the hair dye

[0136] As a comparative example, a natural oil containing 50% or more unsaturated groups and an oil derivative were directly mixed and applied to a hair dye.

[0137] Specifically, the first agent of the oxidative hair dye is prepared by heating purified water to 70°C, then adding each component in turn and stirring and dissolving, cooling to below 50°C, and then adding the components after monoethanol. The second agent is prepared by heating purified water to 70°C, then adding each component in turn and stirring and dissolving, cooling to below 45°C, and then adding hydrogen peroxide and stirring.

[0138] The following Table 8 shows the first oxidative hair dye, and Table 9 shows the second oxidative hair dye.

[0139] [Table 8]

[0140]

[0141] [Table 9]

[0142] Element Comparative Example Purified water Up to 100% by weight Cetearyl Alcohol 3.00 Polyoxyethylene lauryl ether 0.80 etidronic acid 0.10 Phosphoric acid 0.10 Sodium monohydrogen phosphate 0.20 Hydrogen peroxide water 6.0 pH 3.3

[0143] The first agent of Table 8 and the second agent of Table 9 prepared as described above were thoroughly mixed at a ratio of 1:1, and then applied to the hair, left for 30 minutes, and then washed to perform dyeing.

[0144] (1) Friction Coefficient (Surface Friction Coefficient) Measurement

[0145] 4 g of each dyed hair was fixed on an acrylic tress, and then measured using a tensile strength tester (MTT 175). The results are shown in the following Table 10. The smaller the value, the smoother the surface.

[0146] [Table 10]

[0147]

[0148] (2) Measurement of Combing Force

[0149] 4 g of each dyed hair was fixed on an acrylic hair bundle, and then measured using a tensile strength tester (MTT 175), and the results are shown in the following Table 11. The smaller the value, the easier it is to comb the hair without tangling.

[0150] [Table 11]

[0151]

[0152] (3) Color fading comparison test after shampooing

[0153] SLES 6% solution was applied to dyed hair at 1 / 10 of the sample weight, and then washed repeatedly under the same conditions. The flow rate during washing was 30 ml / s, foaming for 15 seconds, massage for 40 seconds and washing for 60 seconds. Assuming washing for 4 weeks, a total of 28 times of washing. The experimental results of measuring ΔE values ​​are shown in Table 12 below. The smaller the ΔE value, the smaller the color change of fading.

[0154] [Table 12]

[0155]

[0156] (4) Panelists’ evaluation of hair damage after dyeing

[0157] 15 professional panelists evaluated the dyed hair by hand combing, smoothness and other tactile evaluations, and gave higher scores as the hair felt less damaged. The results are shown in the following Table 13. The evaluation was based on a 5-point scale, and the smaller the value, the easier it is to comb the hair without tangling.

[0158] [Table 13]

[0159]

[0160] 2. Prepare the hair dye, oxidation initiator and oil separately and mix them just before use

[0161] The hair dye, oxidation initiator and oil were prepared separately and mixed just before use as shown in Tables 14 to 16. Table 14 shows the first oxidation hair dye, Table 15 shows the second oxidation hair dye, and Table 16 shows the third oil.

[0162] Specifically, the first agent of the oxidative hair dye is prepared by heating purified water to 70°C, then sequentially adding each component and stirring to dissolve, cooling to below 50°C, and then adding the component after monoethanol. The second agent is prepared by heating purified water to 70°C, then sequentially adding each component and stirring to dissolve, cooling to below 45°C, and then adding hydrogen peroxide and stirring.

[0163] [Table 14]

[0164]

[0165] [Table 15]

[0166]

[0167] [Table 16]

[0168]

[0169] Test methods, effects of the present invention and experimental results (Examples and Comparative Examples 2-1 to 3)

[0170] Immediately before use, the Example and Comparative Example 3 agents were thoroughly mixed and stirred in the above-prepared Agents 1 and 2 in a 1:1 ratio, and then applied to the hair, left for 30 minutes, and then washed to perform dyeing.

[0171] (1) Friction coefficient (surface friction coefficient) measurement

[0172] 4 g of each dyed hair was fixed on an acrylic hair bundle, and then measured using a tensile strength tester (MTT 175). The results are shown in the following Table 17. The smaller the value, the smoother the surface.

[0173] [Table 17]

[0174]

[0175] (2) Measurement of Combing Force

[0176] 4 g of the dyed hair was fixed on an acrylic hair bundle, and then measured using a tensile strength tester (MTT 175). The results are shown in the following Table 18. The smaller the value, the easier it is to comb the hair without tangling.

[0177] [Table 18]

[0178]

[0179] (3) Color fading comparison test after shampooing

[0180] SLES 6% solution was applied to dyed hair at 1 / 10 of the sample weight, and then washed repeatedly under the same conditions. The flow rate during washing was 30 ml / s, foaming for 15 seconds, massage for 40 seconds and washing for 60 seconds. Assuming washing for 4 weeks, a total of 28 times of washing. The experimental results of measuring ΔE values ​​are shown in Table 19 below. The smaller the ΔE value, the smaller the color change of fading.

[0181] [Table 19]

[0182]

[0183] (4) Panelists’ evaluation of hair damage after dyeing

[0184] 15 professional panelists evaluated the dyed hair by hand combing, smoothness and other tactile evaluations, and gave higher scores as the hair felt less damaged. The results are shown in the following Table 20. The evaluation was based on a 5-point scale, and the smaller the value, the easier it is to comb the hair without tangling.

[0185] [Table 20]

[0186]

[0187] As can be judged from the above results, it can be confirmed that a hair dye can be prepared by using a natural oil or its derivative having at least one double bond and an unsaturated oil group accounting for more than 50% of the entire oil composition and an oxidation initiator to minimize hair damage and improve the color durability after dyeing.

[0188] 3. Examples of preferred decolorizing agents according to the present invention

[0189] As a preferred embodiment of the present invention, decolorizing agents were prepared as described in the following Tables 21 to 23. Table 21 shows the first decolorizing agent, Table 22 shows the second decolorizing agent, and Table 23 shows the third oil.

[0190] [Table 21]

[0191] Classification (weight %) content Purified water Up to 100% by weight EDTA·4Na 0.2 Propylene glycol 3.00 Sodium sulfite 0.70 Cetyl Alcohol 4.00 Stearyl Alcohol 2.00 Stearyltrimethylammonium chloride 2.50 Polyoxyethylene cetyl ether 2.50 Monoethanolamine 6.00 pH 10.3

[0192] [Table 22]

[0193] Element content Purified water Up to 100% by weight Cetearyl Alcohol 3.00 Polyoxyethylene lauryl ether 0.80 etidronic acid 0.10 Phosphoric acid 0.10 Sodium monohydrogen phosphate 0.20 Hydrogen peroxide water 6.0 pH 3.3

[0194] [Table 23]

[0195] Classification (weight %) content olive oil 2.0

Claims

1. Use of a preparation comprising an oxidation initiator, an oil containing an olefinic unsaturated hydrocarbon and an oxidation dye in the preparation of a hair product, wherein: The oxidation dye is in the first agent, The oxidation initiator is in the second agent, The oil containing olefinic unsaturated hydrocarbons is separated and contains, respectively, in the third agent, The oxidative initiator is one or more selected from the group consisting of hydrogen peroxide, sodium perborate, sodium percarbonate, ammonium persulfate, bismaleimidoethoxyethane, calcium peroxide, ferric chloride, hypochlorous acid, laccase, magnesium peroxide, MEK (methyl ethyl ketone) peroxide, melanin peroxide, ozonized turpentine, phthalimidoperoxycaproic acid, potassium bromate, potassium kaluate, potassium chlorate, potassium monopersulfate, potassium persulfate, PVP-hydrogen peroxide, sodium bromate, sodium carbonate peroxide, sodium iodate, sodium perborate, sodium persulfate, strontium peroxide, urea peroxide and zinc peroxide.

2. The use according to claim 1, characterized in that: The oxidation dye is one or more selected from the group consisting of phenylenediamine, aminophenol, resorcinol, aminocresol, methylhydroxyethylaminophenol, nitrobenzenediamine and toluenediamine sulfate.

3. The use according to claim 1, characterized in that: The olefinic unsaturated hydrocarbon is an unsaturated fatty acid.

4. The use according to claim 1, characterized in that: The oil containing olefinic unsaturated hydrocarbons is one or more selected from the group consisting of olive oil, macadamia oil, jojoba oil, meadowfoam oil, argan oil, camellia oil, grape seed oil, sunflower oil, avocado oil, canola oil, corn oil, cottonseed oil, hempseed oil, flaxseed oil, linseed oil, palm oil, peanut oil, safflower oil and soybean oil.

5. The use according to claim 1, characterized in that: The first, second and third agents are mixed and applied to the hair just before use.

6. The use according to claim 1, characterized in that: The oxidative initiator promotes a thiol-ene reaction between cysteic acid present in the hair and the olefinically unsaturated hydrocarbon.

7. The use according to claim 1, characterized in that: The hair product has one or more effects selected from the group consisting of hair protection, hair repair, conditioning feel imparting, hair oxidation prevention, dyeing damage prevention and color durability effects.

8. A non-therapeutic hair treatment method, wherein: include: In order to obtain one or more effects selected from the group consisting of hair protection, hair repair, conditioning, hair oxidation prevention, dyeing damage prevention and color durability, hair is treated with a preparation containing an oxidation initiator, an oil containing an olefinic unsaturated hydrocarbon and an oxidation dye, wherein: The oxidation dye is in the first agent, The oxidation initiator is in the second agent, The oil containing olefinic unsaturated hydrocarbons is separated and contains, respectively, in the third agent, The oxidative initiator is one or more selected from the group consisting of hydrogen peroxide, sodium perborate, sodium percarbonate, ammonium persulfate, bismaleimidoethoxyethane, calcium peroxide, ferric chloride, hypochlorous acid, laccase, magnesium peroxide, MEK (methyl ethyl ketone) peroxide, melanin peroxide, ozonized turpentine, phthalimidoperoxycaproic acid, potassium bromate, potassium kaluate, potassium chlorate, potassium monopersulfate, potassium persulfate, PVP-hydrogen peroxide, sodium bromate, sodium carbonate peroxide, sodium iodate, sodium perborate, sodium persulfate, strontium peroxide, urea peroxide and zinc peroxide.

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