JP2009274968A - Hairdye composition containing protein nanoparticles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hairdye composition containing protein nanoparticles exhibiting high safety, having high transparency because of small particle diameters and exhibiting good penetrability to the scalp and follicle. <P>SOLUTION: The hairdye composition contains (a) one or more kinds of hairdye or a constituent component thereof, and (b) the protein nanoparticles having a 10-200 nm average particle size. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hair dye composition containing protein nanoparticles.

  In today's aging society, the degree of advancement of senior citizens into society has increased greatly. For this reason, in the field of cosmetics, the demand for products for elderly people such as hair dyes is growing significantly.

  As hair dyes for dyeing hair, “temporary hair dyes”, “semi-permanent hair dyes”, and “permanent hair dyes” are widely used. In particular, “permanent hair dyes” are particularly versatile. Among these, “oxidative hair dyes” that develop colors by causing an oxidant to act on an oxidative dye precursor (sometimes simply referred to as an oxidative dye) are paraffins. Oxidative hair dyes using oxidative dye precursors such as phenylenediamine have been widely used because of their excellent hair dyeing power and fastness and a variety of colors. These oxidative hair dyes mainly swell the hair under alkaline conditions, open cuticles to infiltrate various oxidative dye precursors into the hair, and oxidatively polymerize by using an oxidant such as hydrogen peroxide. Although the color is developed, the degree of polymerization differs depending on the combination and blending ratio of the dyes, and the color of the polymer also changes. Therefore, various color tones can be obtained. Since the degree of polymerization is different, pigments of various sizes are generated inside the hair. In general, pigment molecules that have become larger due to polymerization become larger than the gaps between the cuticles that have passed when the dye penetrates into the hair before polymerizing and do not flow out of the hair. It is said that it is good.

  However, in practice, the hair color gradually changes or fades away. In addition to the ultraviolet rays of sunlight, the heat of the dryer, etc., this may be caused by the fact that the dye gradually flows out at each shampoo. In addition, when the hair gets wet with sweat or the like, the pigment flows out, and there is a problem that the area around the collar of the clothes is stained. In addition, shampoos that improve color retention have been developed for hair dyes, but sufficient effects have not yet been obtained.

  On the other hand, various demands are made on the quality of “semi-permanent hair dye”. Among them, one of the demands that are particularly demanded and technically difficult to solve is hair damage caused by hair dyes, uniform hair dyeing, and fastness thereof. Efforts to prevent hair damage, to achieve uniform hair coloring and toughness have been focused on the development of hair dye materials so far, and have not been improved by formulation-like devices. .

  Such non-uniform remedies include, for example, uniform hair dyeing by increasing the viscosity of the system and improving adhesion, and increasing the amount of surfactant to improve the wetting characteristics of the hair surface. In the dyeing, a means for promoting penetration of the dye into the hair using a penetration enhancer such as benzyl alcohol has been developed. However, the means for increasing the viscosity of the system may impair the usability, and an increase in the amount of surfactant may be unfavorable in terms of safety, and benzyl alcohol, which is a penetration enhancer, points out problems in terms of safety or environmental science. It has been pointed out that the content needs to be reduced.

  On the other hand, protein nanoparticles are a material attracting attention in the field of drug delivery system (DDS), and application to cosmetics has also been proposed (Patent Document 1). The effect on it has not been known so far.

WO2007 / 114262

  An object of the present invention is to solve the above-described problems of the prior art. That is, the present invention should solve the problem of providing a hair dye composition that improves the fastness of hair dyeing to shampooing, has no or very little hair damage, and enables uniform hair dyeing. It was an issue.

  As a result of diligent research to solve the above problems, the present inventors have improved the fastness of hair dyeing to hair washing by adding protein nanoparticles to the hair dye or its constituent components, and damage the hair. It has been found that there can be provided a hair dye composition that has no or very little hair and enables uniform hair dyeing. The present invention has been completed based on these findings.

  That is, according to the present invention, there is provided a hair dye composition containing (a) one or more hair dyes or components thereof, and (b) protein nanoparticles having an average particle size of 10 to 200 nm. The

Preferably, the hair dye is a dye.
Preferably, the hair dye is an oxidative hair dye.
Preferably, the oxidative hair dye is a combination of an oxidative dye precursor and an oxidant.
Preferably, the content of protein nanoparticles is 0.01 to 50% by weight based on the weight of the composition.

  Preferably, the protein is at least one selected from the group consisting of collagen, gelatin, acid-treated gelatin, albumin, ovalbumin, casein, transferrin, globulin, fibroin, fibrin, laminin, fibronectin, or vitronectin.

Preferably, the hair dye composition of the present invention further contains 0.1 to 100% by weight of a hair active ingredient based on the weight of the protein.
Preferably, the active hair ingredient is a fragrance, an antibacterial agent, a softener, a moisturizer, an ultraviolet absorber, an active oxygen scavenger, an antioxidant, a hair restorer, an amino acid, a mineral, or an antimicrobial agent.
Preferably, the active hair active ingredient is an ionic substance or a fat-soluble substance.

Preferably, the hair dye composition of the present invention has an ethanol content of 20% by weight or less.
Preferably, the protein is cross-linked during and / or after nanoparticle formation.
Preferably, the crosslinking treatment is performed using an enzyme.

Preferably, the hair dye composition of the present invention includes casein nanoparticles prepared by the following steps (a) to (c).
(A) mixing casein with a basic aqueous medium having a pH of 8 or more and less than 11;
(B) adding at least one hair active ingredient to the solution obtained in step (a); and (c) injecting the solution obtained in step (b) into an acidic aqueous medium having a pH of 3.5 to 7.5. :

Preferably, the hair dye composition of the present invention includes casein nanoparticles prepared by the following steps (a) to (c).
(A) mixing casein with a basic aqueous medium having a pH of 8 or more and less than 11;
(B) adding at least one hair active ingredient to the solution obtained in step (a); and (c) stirring the solution obtained in step (b) while adjusting the pH of the solution from the isoelectric point. Lowering to pH 1 or more away:

  Furthermore, according to this invention, the hair dyeing method of hair including the process of apply | coating the hair dye composition of this invention mentioned above to hair is provided.

  Since the protein nanoparticles in the hair dye composition of the present invention are nano-sized, and have high affinity with hair, the fastness of hair dyeing to hair washing is improved, and there is no or very little hair damage. In addition, uniform hair dyeing is possible. In the present invention, since natural protein nanoparticles are used, safety is high.

Hereinafter, embodiments of the present invention will be described more specifically.
The hair dye composition of the present invention comprises (a) one or more hair dyes or constituents thereof, and (b) protein nanoparticles having an average particle size of 10 to 200 nm. The hair dye composition of the present invention preferably contains 0.01 to 50% by weight of protein nanoparticles, more preferably 0.1 to 10% by weight of protein nanoparticles, based on the weight of the composition. More preferably 0.5 to 5% by weight of protein nanoparticles, particularly preferably 1 to 3% by weight of protein nanoparticles.

  The average particle size of the casein nanoparticles of the present invention is usually 10 to 200 nm, preferably 10 to 100 nm, more preferably 10 to 50 nm, and particularly preferably 15 to 30 nm.

  The hair dye used in the present invention may be a temporary hair dye, a semi-permanent hair dye, or a permanent hair dye. As temporary hair dyes and semi-permanent hair dyes, dyes can be directly blended, and one or more known ones such as tar-based pigments and natural pigments can be used in combination. Among them, nitro dyes, azo dyes, nitroso dyes, triphenylmethane dyes, xanthene dyes, quinoline dyes, anthraquinone dyes or indigo dyes are preferable because they can provide a good hair dyeing effect, and more preferably Orange No. 205. , Black 401, Purple 401, Red 102, Red 227, Red 106, Red 504, Yellow 203, Yellow 403 (1), Green 204, Carbon black, Black titanium oxide, Henna, Iron oxide , Tar dyes, chlorophyll, pigments and the like.

  As the permanent hair dye, an oxidative hair dye can be used. The oxidative hair dye usually takes the form of a two-agent form consisting of a first agent containing an oxidative dye precursor and a second agent containing an oxidant. In the present invention, protein nanoparticles are those 2 You may mix | blend with any of the structural units of the oxidative hair dye of an agent form (namely, either 1st agent, 2nd agent, or both). In addition, “the component” in “hair dye or component thereof” as used in the present specification refers to, for example, the first agent or the second agent when the hair dye is in the form of two agents as described above. Means. In addition, the present invention can be applied to a one-component oxidative hair dye.

  That is, the composition for oxidative hair dye of the present invention is a form in which protein nanoparticles are blended with the first part of a two-part oxidative hair dye, a form in which protein nanoparticles are blended with the second part, and the first part And any form of the form which mix | blended the protein nanoparticle with the 2nd agent, or the form which mix | blended the protein nanoparticle with the 1 agent type oxidative hair dye can be taken. In addition to the above-mentioned essential components, other components that are usually blended in the oxidative hair dye are blended with the oxidative hair dye composition of the present invention within a range that does not impair the intended effect of the present invention. can do.

  For example, in the two-component oxidative hair dye, the oxidative dye precursor blended in the first agent includes phenylenediamines, aminophenols, toluylenediamines, aminonitrophenols, diaminopyridines or these Examples thereof include salts.

  The compounding quantity of these oxidation dye precursors in the hair dye composition of this invention is about 0.01 weight% or more and 10.0 weight% or less normally with respect to the whole composition. As a coupler, for example, resorcin, metaaminophenol, metaphenylenediamine and the like can be blended together with a corresponding oxidation dye precursor.

  Further, in the first agent, for example, surfactants such as polyoxyethylene alkyl ether salts and polyoxyethylene alkylamine fatty acid amides; humectants such as glycerin and propylene glycol; oil components such as lanolin and liquid paraffin; sulfites, Stabilizers such as ascorbic acid; thickeners such as carboxymethylcellulose and carboxyvinyl polymer; alkaline agents such as ammonia water, monoethanolamine, sodium hydroxide, and potassium hydroxide; higher alcohols, fragrances, and the like can be blended.

  On the other hand, hydrogen peroxide is usually used as the oxidizing agent for the second agent, but in this second agent, for example, stabilizers such as tarpinal and sodium stannate; fats and oils such as paraffin; higher alcohols, surface activity Agents, acids, pH adjusters, fragrances and the like can be blended. Such a two-component oxidative hair dye composition of the present invention is usually used for hair dyeing for 10 to 30 minutes by mixing the first agent and the second agent immediately before use.

  In addition, in the one-component type oxidative hair dye, for example, components such as 2,4-diaminophenol sulfate, stearyltrimethylammonium chloride / triethanolamine, ammonium thioglycolate, propylene diglycol, and LPG (gas) are essential as described above. It can be blended in addition to the ingredients.

  The hair dye composition of the present invention preferably contains 0.1 to 100% by weight of an active ingredient for hair based on the weight of protein, and is 0.1 to 50% by weight based on the weight of protein. More preferably, it contains an active ingredient for hair.

  In the present invention, the hair active ingredient may be added at the time of forming the protein nanoparticles, or may be added after the formation of the nanoparticles.

  Although the kind of active hair ingredient used by this invention is not specifically limited, For example, it can select from a cosmetic ingredient, a quasi-drug ingredient, or a pharmaceutical ingredient. In the present invention, specific examples of active hair ingredients contained in protein nanoparticles include fragrances, antibacterial agents, softeners, moisturizers, ultraviolet absorbers, active oxygen removers, antioxidants, hair restorers, amino acids , Minerals, or antimicrobial agents.

  Air fresheners include musk, acacia oil, anise oil, ylang ylang oil, cinnamon oil, jasmine oil, sweet orange oil, spearmint oil, geranium oil, thyme oil, neroli oil, peppermint oil, hinoki oil, fennel oil, peppermint oil Bergamot oil, lime oil, lavender oil, lemon oil, lemongrass oil, rose oil, rosewood oil, anisaldehyde, geraniol, citral, cybeton, muscone, limonene, vanillin and the like.

  Antibacterial agents include piroctone olamine, isopropyl methyl ether, hinokitiol, zinc pyrithione, climbazole, benzalkonium chloride, photosensitive dye 101, chlorhexidine, salicylic acid, phenol, ketoconazole and miconazole, sulfur, triclosan, trichlorocarbanilide, chlorhexidine Hydrochloride, Chlorhexidine gluconate, Halocarban, Chlorophenesin, Benzethonium chloride, Benzalkonium chloride, Lysozyme chloride, Alkyldiaminoethylglycine hydrochloride, Isopropylmethylphenol, Benzoic acid, Photosensitizer 201, Thymol, Hexachlorophene, Berberine Thioxolone, yukinoshita extract, buckwheat extract, buckwheat extract and their derivatives and salts.

  Softeners include glycerin, mineral oil, emollient ingredients (eg, isopropyl isostearate, polyglyceryl isostearate, isotridecyl isononanoate, octyl isononanoate, oleic acid, glyceryl oleate, cocoa butter, cholesterol, mixed fatty acid triglycerides, dioctyl succinate) Sucrose acetate stearate, cyclopentasiloxane, sucrose distearate, octyl palmitate, octyl hydroxystearate, aralkyl behenate, sucrose polybehenate, polymethylsilsesquioxane, myristyl alcohol, cetyl myristate, myristyl myristate, laurin Acid hexyl) and the like.

  Examples of the humectant include agar, diglycerin, distearyldimonium hectorite, butylene glycol, polyethylene glycol, propylene glycol, hexylene glycol, yokinein extract, petrolatum, urea, hyaluronic acid, ceramide, lipid, isoflavone, amino acid, Collagen, mucopolysaccharide, fucodyne, lactoferrin, sorbitol, chitin / chitosan, malic acid, glucuronic acid, placenta extract, seaweed extract, bopipi extract, amacha extract, hypericum extract, coleus extract, masaki extract, kouca extract, maika flower extract, cho Ray extract, hawthorn extract, rosemary extract, Duke extract, chamomile extract, nettle extract, litchi extract, yarrow extract, allo Extract, horse chestnut extract, Asunaroekizu, Fucus extract, Osmo-in extract, oat extract, tuberosa polysaccharide, Cordyceps extract, barley extract, orange extract, mention may be made of Rehmannia glutinosa, pepper extract, and Yokuininekisu. In the case of casein nanoparticles, casein itself has moisture retention.

  Examples of UV inhibitors include homomenthyl salicylate, 2-methoxyhexycin 2-ethylhexyl, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone sulfonic acid, 2-hydroxy-4-methoxybenzophenone sulfonic acid Examples thereof include sodium, 4-t-butyl-4′-methoxy-dibenzoylmethane, titanium oxide, and zinc oxide.

  Active oxygen scavengers include carotenoids such as superoxide dismutase (SOD), mannitol, beta carotene, astaxanthin, rutin and derivatives thereof, bilirubin, cholesterol, tryptophan, histidine, quercetin, quercitrin, catechin, catechin derivatives, gallic acid , Gallic acid derivatives, Ogon extract, Ginkgo biloba extract, Yukinoshita extract, Melissa extract, Gennoshoco extract, Botpi extract, Parsley extract, Tormentilla extract, Rakan fruit extract, Seaweed extract, Yashajitsu extract, Zicopi An extract etc. are mentioned.

  Examples of the antioxidant include carotenes, retinoic acid, retinol, vitamin C and derivatives thereof, kinetin, astaxanthin, tretinoin, vitamin E and derivatives thereof, sesamin, α-lipoic acid, coenzyme Q10, flavonoids, erythorbic acid, Examples thereof include propyl gallate, BHT (di-n-butylhydroxytoluene), BHA (butylhydroxyanisole), koki extract, soybean extract, black tea extract, tea extract, and age extract.

  Hair restorer is glycyrrhetinic acid or its derivative, glycyrrhizic acid or its derivative, hinokitiol, minoxidil or its analog, adenosine, vitamin E or its derivative, vitamin C derivative, 6-benzylaminopurine, benzyl nicotinate, tocopherol nicotinate, Nicotinic acid β-butoxy ester, isopropylmethylphenol, pentadecanoic acid or derivatives thereof, cephalatin, finasteride, t-flavanone, pantothenic acid, panthenol, licorice extract, quince isoform extract, cucumber extract, assembly extract, red pepper extract , Toucha extract, carrot extract, spinach extract, button extract, mandarin extract and the like.

  Examples of amino acids include glutamic acid, L-aspartic acid, L-alanine, L-cysteine, glycine, L-isoleucine, L-leucine, lysine, and the like, and salts thereof. Known minerals and antimicrobial agents can be used as appropriate.

  The active hair active ingredients described above may be used alone or in combination of two or more.

  In the present invention, it has been found that the active hair component can be encapsulated in the casein nanoparticles by utilizing the interaction between the fat-soluble active hair component and the hydrophobic casein moiety. Furthermore, it was found that these particles exist stably in an aqueous solution. As a fat-soluble substance, ClogP is preferably larger than 0, more preferably ClogP is 1 or more.

  It has also been found that the active ingredient of ionic hair is encapsulated by mixed particles of protein and ionic polysaccharide or another type of ionic protein.

  The type of protein used in the present invention is not particularly limited, but a protein having a lysine residue and a glutamine residue is preferable, and a protein having a molecular weight of about 10,000 to 1,000,000 is preferably used. The origin of the protein is not particularly limited, but it is preferable to use a human-derived protein. Specific examples are listed as proteins, but the present invention is not limited to these compounds. At least one selected from the group consisting of collagen, gelatin, acid-treated gelatin, albumin, ovalbumin, casein, keratin, sericin, zein, transferrin, globulin, fibroin, fibrin, laminin, fibronectin, or vitronectin can be used. In addition, the origin of the protein is not particularly limited, and any of cows, pigs, fish, and gene recombinants can be used. As the genetically modified gelatin, for example, those described in EU1014176A2 and US Pat. No. 6,992,172 can be used, but are not limited thereto. Among them, casein, acid-treated gelatin, collagen, or albumin is preferable, and casein or acid-treated gelatin is most preferable.

  When casein is used in the present invention, the origin of casein is not particularly limited, and may be derived from milk or bean, α-casein, β-casein, γ-casein, κ-casein and theirs. Mixtures can be used. Genetically modified organisms can also be used. Preferably, casein sodium can be used. Casein can be used alone or in combination of two or more.

  The proteins used in the present invention may be used alone or in combination of two or more.

  In the present invention, the protein can be crosslinked during and / or after the formation of the nanoparticles. An enzyme can be used for the above-described crosslinking treatment. The enzyme is not particularly limited as long as it has a known protein cross-linking effect, and transglutaminase is preferable among them.

  Transglutaminase may be derived from a mammal or a microorganism, and a genetic recombinant can be used. Specifically, Activa series manufactured by Ajinomoto Co., Inc., transglutaminases derived from mammals that have been released as reagents, for example, guinea pig liver-derived trans from Oriental Yeast Co., Ltd., Upstate USA Inc., Biodesign International, etc. Examples include glutaminase, goat-derived transglutaminase, rabbit-derived transglutaminase, and human-derived recombinant transglutaminase.

  The amount of the enzyme used for the crosslinking treatment in the present invention can be appropriately set according to the type of protein, but is typically about 0.1 to 100% by weight based on the weight of the protein. It can be added, and preferably about 1 to 50% by weight can be added.

  The time for the cross-linking reaction by the enzyme can be appropriately set according to the kind of protein and the size of the nanoparticle, but it can be reacted normally for 1 hour to 72 hours, preferably 2 hours to 24 hours. Can react.

  The temperature of the cross-linking reaction by the enzyme can be appropriately set according to the type of protein and the size of the nanoparticles, but it can be reacted at 0 to 80 ° C., preferably 25 to 60 ° C. Can react at ℃.

  The enzyme used for this invention can be used individually or in combination of 2 or more types.

  The nanoparticles of the present invention should be prepared according to the method described in Japanese Patent Application Laid-Open No. 6-79168 or by C. Coester, Journal Microcapsulation, 2000, Vol. 17, p. 187-193. However, it is preferable to use an enzyme instead of glutaraldehyde as a crosslinking method.

Moreover, in this invention, it is preferable to perform an enzyme crosslinking process in an organic solvent. The organic solvent used here is preferably a water-soluble organic solvent such as ethanol, isopropanol, acetone, or THF.
Furthermore, in the present invention, it is preferable to disperse the organic solvent after the crosslinking treatment and disperse in water. Water may be added before the organic solvent is distilled off, or water may be added after the distillation.

  One or more components selected from lipids (phospholipids, etc.), ceramides, anionic polysaccharides, cationic polysaccharides, anionic proteins, cationic proteins, or cyclodextrins are added to the hair dye composition of the present invention. You can also. The amount of lipid (such as phospholipid), anionic polysaccharide, cationic polysaccharide, anionic protein, cationic protein, and cyclodextrin is not particularly limited, but is generally 0.1 to 100 weight with respect to the weight of the protein. % Can be added. In the hair dye composition of the present invention, the sustained release rate can be adjusted by changing the ratio of the above components to the protein.

  Specific examples are listed as phospholipids that can be used in the present invention, but the present invention is not limited to these compounds. Examples include phosphatidylcholine (lecithin), phosphatidylethanolamine, phosphatidylserine, phosphatidylinositol, phosphatidylglycerol, diphosphatidylglycerol, sphingomyelin and the like.

  The anionic polysaccharide that can be used in the present invention is a polysaccharide having an acidic polar group such as a carboxyl group, a sulfate group, or a phosphate group. Specific examples are listed below, but the present invention is not limited to these compounds. Examples thereof include chondroitin sulfate, dextran sulfate, carboxymethylcellulose, carboxymethyldextran, alginic acid, pectin, carrageenan, fucoidan, agaropectin, porphyran, caraya gum, gellan gum, xanthan gum, and hyaluronic acid.

  The cationic polysaccharide that can be used in the present invention is a polysaccharide having a basic polar group such as an amino group. Specific examples are listed below, but the present invention is not limited to these compounds. Examples thereof include glucosamine such as chitin and chitosan and galactosamine as a constituent monosaccharide.

  Anionic proteins that can be used in the present invention are proteins and lipoproteins whose isoelectric point is more basic than physiological pH. Specific examples are listed, but the present invention is not limited to these compounds. Examples include polyglutamic acid, polyaspartic acid, lysozyme, cytochrome C, ribonuclease, trypsinogen, chymotrypsinogen, α-chymotrypsin and the like.

  The cationic proteins used in the present invention are proteins and lipoproteins whose isoelectric point is on the acidic side of physiological pH. Specific examples are listed, but the present invention is not limited to these compounds. Examples include polylysine, polyarginine, histone, protamine, and ovalbumin.

In the present invention, casein nanoparticles prepared by the following steps (a) to (c) can be used.
(A) mixing casein with a basic aqueous medium having a pH of 8 or more and less than 11;
(B) adding at least one hair active ingredient to the solution obtained in step (a); and (c) injecting the solution obtained in step (b) into an acidic aqueous medium having a pH of 3.5 to 7.5. :

Furthermore, in the present invention, casein nanoparticles prepared by the following steps (a) to (c) can be used.
(A) mixing casein with a basic aqueous medium having a pH of 8 or more and less than 11;
(B) adding at least one hair active ingredient to the solution obtained in step (a); and (c) stirring the solution obtained in step (b) while adjusting the pH of the solution from the isoelectric point. Lowering to pH 1 or more away:

In the present invention, casein nanoparticles of a desired size can be produced. Further, the active hair component can be encapsulated in the casein nanoparticles by utilizing the interaction between the hydrophobic active hair component and the hydrophobic casein moiety. Furthermore, it was found that these particles exist stably in an aqueous solution.
It has also been found that mixed particles of casein and ionic polysaccharides or other types of ionic proteins encapsulate ionic hair active ingredients.

  The method for producing casein nanoparticles of the present invention includes a method in which casein is mixed into a basic aqueous medium solution and injected into the basic aqueous medium solution, a casein is mixed into the basic aqueous medium solution, and the pH is adjusted while stirring. A method of lowering is mentioned.

  As a method of mixing casein into a basic aqueous medium liquid and injecting it into the basic aqueous medium, it is convenient and preferable to use a syringe, but especially if it is a method satisfying the injection speed, solubility, temperature, and stirring state. Not limited. In general, the injection rate can be from 1 mL / min to 100 mL / min. The temperature of the basic aqueous medium can be appropriately set, but can be normally 0 ° C. to 80 ° C., and preferably 25 ° C. to 70 ° C. Although the temperature of an aqueous medium can be set suitably, it can be normally 0 to 80 degreeC, Preferably it can be 25 to 60 degreeC. The stirring speed can be set as appropriate, but it can be normally set to 100 rpm to 3000 rpm, and preferably 200 rpm to 2000 rpm.

  As a method of lowering the pH while mixing casein with a basic aqueous medium solution and stirring, it is convenient and preferable to add acid dropwise, but it is particularly limited as long as the method satisfies the solubility, temperature, and stirring state. do not do. The temperature of the basic aqueous medium can be appropriately set, but can be normally 0 ° C. to 80 ° C., and preferably 25 ° C. to 70 ° C. The stirring speed can be set as appropriate, but it can be normally set to 100 rpm to 3000 rpm, and preferably 200 rpm to 2000 rpm.

  As the aqueous medium used in the present invention, an organic acid or base, an aqueous solution of an inorganic acid or inorganic base, or a buffer solution can be used.

  Specifically, citric acid, ascorbic acid, gluconic acid, carboxylic acid, tartaric acid, succinic acid, acetic acid or phthalic acid, trifluoroacetic acid, morpholinoethanesulfonic acid, 2- [4- (2-hydroxyethyl) -1- Piperazinyl] organic acids such as ethanesulfonic acid; organic bases such as tris (hydroxymethyl), aminomethane, ammonia; inorganic acids such as hydrochloric acid, perchloric acid, carbonic acid; sodium phosphate, potassium phosphate, calcium hydroxide, Although the aqueous solution using inorganic bases, such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide, is mentioned, It is not limited to these.

  The concentration of the aqueous medium used in the present invention is preferably about 10 mM to about 1M. More preferably, it is about 20 mM to about 200 mM.

  The pH of the basic aqueous medium used in the present invention is preferably 8 or more, and preferably 8 to 12. More preferably, the pH is 10-12. If the pH is too high, there is a concern about hydrolysis and danger in handling, so the above range is preferable.

  In the present invention, the temperature at which casein is mixed with a basic aqueous medium having a pH of 8 or more is preferably from 0 to 90 ° C, more preferably from 10 to 80 ° C. More preferably, it is 20-70 degreeC.

  The pH of the acidic aqueous medium used in the present invention is preferably 3.5 to 7.5. More preferably the pH is from 5 to 6. Outside the above range, the particle size tends to increase.

  The hair dye composition of the present invention may contain a treatment agent. Although it does not specifically limit as a treatment agent, One or more types selected from a cationic activator, silicone, hydrolyzed protein, oil, phospholipid polymer, and ceramide can be used.

  Specific examples are listed as cationic activators that can be used in the present invention, but the present invention is not limited to these compounds. Examples include stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, behentrimethylammonium chloride, stearyltrimethylammonium bromide, cetyltrimethylammonium bromide, dicocodimonium chloride and the like.

  Specific examples are listed as oils that can be used in the present invention, but the present invention is not limited to these compounds. Examples include camellia oil, salamander seed fat, macadamia nut oil, rice germ oil, mink oil, and palm oil.

  Specific examples of silicones that can be used in the present invention are listed, but the present invention is not limited to these compounds. Examples thereof include dimethicone, dimethiconol, phenyltrimethicone, cyclopentasiloxane, cyclomethicone, aminopropyl dimethicone, amodimethicone, and a copolymer thereof.

  The hair dye composition of the present invention may further contain an additive. Although it does not specifically limit as an additive, One or more types selected from a pearl luster material, antiseptic | preservative, antioxidant, a pigment | dye agent, a thickener, or a pH adjuster can be used. Furthermore, higher alcohols (such as cetanol and stearyl alcohol), animal / vegetable oils and fats, benzyl alcohol, and hydroxyethyl cellulose may be added as necessary.

  Specific examples are listed as nacreous materials that can be used in the present invention, but the present invention is not limited to these compounds. Examples include ethylene glycol distearate, ethylene glycol monostearate, mica coated with guanine and titanium dioxide, bismuth oxychloride, and monoethanolamide stearate.

  Specific examples are listed as preservatives that can be used in the present invention, but the present invention is not limited to these compounds. Benzoic acid, sodium benzoate, paraben, ethyl paraben, methyl paraben, propyl paraben, butyl paraben, potassium sorbate, sodium sorbate, sorbic acid, sodium dehydroacetate, hydrogen peroxide, formic acid, ethyl formate, sodium dichlorite, Propionic acid, sodium propionate, calcium propionate, pectin degradation product, polylysine, phenol, isopropylmethylphenol, orthophenylphenol, phenoxyethanol, resorcin, dibutylhydroxytoluene (BHT), thymol, thiram, tea tree oil, hinokitiol, glycerin, di Propylene glycol, 1.3-butylene glycol, 1.4-butylene glycol, 1,2 pentanediol, 2-methyl-2,4-pentanediol, etc. That.

  Specific examples are listed as antioxidants that can be used in the present invention, but the present invention is not limited to these compounds. Vitamin A, retinoic acid, retinol, retinol acetate, retinol palmitate, retinyl acetate, retinyl palmitate, tocopheryl retinoic acid, vitamin C and its derivatives, kinetin, β-carotene, astaxanthin, lutein, lycopene, tretinoin, vitamin E , Α-lipoic acid, coenzyme Q10, polyphenol, SOD, phytic acid and the like.

  Specific examples are listed as coloring agents that can be used in the present invention, but the present invention is not limited to these compounds. Examples include krill pigment, orange pigment, cacao pigment, kaolin, carmine, gunjo, cochineal pigment, chromium oxide, iron oxide, titanium dioxide, tar pigment, chlorophyll and the like.

  Specific examples are listed as thickeners that can be used in the present invention, but the present invention is not limited to these compounds. Quince seed, carrageenan, gum arabic, caraya gum, xanthan gum, gellan gum, tamarind gum, locust bean gum, tragacanth gum, pectin, starch, cyclodextrin, methylcellulose, ethylcellulose, carboxymethylcellulose, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, Examples include sodium polyacrylate.

  Specific examples of the pH adjusting agent that can be used in the present invention are listed, but the present invention is not limited to these compounds. Examples include sodium citrate, sodium acetate, sodium hydroxide, potassium hydroxide, phosphoric acid, and succinic acid.

  The dosage form of the hair dye composition of the present invention is not particularly limited. For example, shampoo, rinse, hair conditioner, hair pack, hair liquid, hair tonic, hair spray, permanent wave composition, body soap, soap, sun care (Sunscreen, sun oil, after sun lotion), fragrance, liquid for external use, poultice, coating agent, wiping agent, bath agent, disinfectant, ointment, gel, cream, plaster, percutaneous absorption type adhesive Tapes, wound protection agents, aerosols, lotions, tonics, liniments, emulsions, suspensions, powders, foams, massage creams, nutrition creams, packs, sheet-type external preparations, makeup cosmetics such as mascara Can be mentioned.

  The method for applying the hair dye composition of the present invention is not particularly limited, but may be wash-off (such as shampoo or conditioner) or leave-on (such as gel, mousse, cream, lotion, spray, or air-injected styling foam). Also good.

The dose of the hair dye composition of the present invention can be appropriately set according to the type and amount of active hair ingredients, the amount of hair of the user, the state, etc. About 1 μg to 50 mg / cm ² can be administered, preferably about 2.5 μg to 10 mg / cm ² can be administered.
The following examples further illustrate the present invention, but the scope of the present invention is not limited to these examples.

Production Example 1:
200 mg of casein (milk-derived, manufactured by Wako Pure Chemical Industries, Ltd.) is mixed with 10 mL of pH 10 and 50 mM citrate buffer. When pH was adjusted to 7 by adding hydrochloric acid, casein nanoparticles were obtained. The average particle size of the particles was 19 nm as measured using a light scattering photometer, Nano-ZS manufactured by Malvern Co., Ltd.

Production Example 2:
Casein Na (milk-derived, manufactured by Wako Pure Chemical Industries, Ltd.) 10 mg is mixed with 1 mL of pH 9 and 50 mM phosphate buffer. Nicotinamide (made by Wako Pure Chemical Industries) 1.5mg is dissolved in ethanol 0.25mL. When hydrochloric acid was added to adjust the pH to 7, an aqueous dispersion of casein nanoparticles encapsulating nicotinamide was obtained. The average particle size of the above particles was 21 nm as measured using a light scattering photometer, Nano-ZS manufactured by Malvern Co., Ltd.

Production Example 3:
Casein Na (milk-derived, manufactured by Wako Pure Chemical Industries, Ltd.) 10 mg is mixed with 1 mL of pH 9 and 50 mM phosphate buffer. Dissolve 1.7 mg of hinokitiol (manufactured by Wako Pure Chemical Industries) in 0.25 mL of ethanol. The hinokitiol solution was dropped into the casein solution while stirring, and 1 mL of this mixed solution was injected into 10 mL of phosphate buffered water at pH 5 and 200 mM using a microsyringe under stirring conditions of 40 ° C. and 800 rpm. An aqueous dispersion of casein nanoparticles encapsulating hinokitiol was obtained. The average particle size of the above particles was 57 nm as measured using a light scattering photometer and a Microtrack manufactured by Nikiso Corp.

Production Example 4:
Casein Na (milk-derived, manufactured by Wako Pure Chemical Industries, Ltd.) 10 mg is mixed with 1 mL of pH 9 and 50 mM phosphate buffer. Tocopherol acetate 0.5 mg is dissolved in ethanol 0.25 mL. The tocopherol acetate solution was added dropwise to the casein solution with stirring, and hydrochloric acid was added to adjust the pH to 7. As a result, an aqueous dispersion of casein nanoparticles encapsulating the tocopherol acetate was obtained. The average particle size of the above particles was 68 nm as measured using a light scattering photometer, Nano-ZS manufactured by Malvern Co., Ltd.

Production Example 5:
Dissolve 10 mg of acid-treated gelatin and 5 mg of TG-S (Ajinomoto) in 1 mL of water. When 1 mL of gelatin solution was injected into 10 mL of ethanol in which 1.7 mg of glycyrrhetinic acid was dissolved using a microsyringe under the external stirring conditions of 40 ° C. and 800 rpm, gelatin nanoparticles were obtained. Allow to stand for 5 hours at an external temperature of 55 ° C. to enzymatically cross-link gelatin nanoparticles. The average particle size of the above particles was 80 nm as measured using a light scattering photometer and a Microtrack manufactured by Nikiso Corp.

  5 mL of water was added to the obtained gelatin nanoparticle dispersion, ethanol was removed by a rotary evaporator, and an aqueous dispersion of gelatin nanoparticles encapsulating glycyrrhetinic acid was obtained. The average particle size of the above particles was 201 nm as measured using a light scattering photometer and a Microtrack manufactured by Nikiso Corp.

Production Example 6:
Dissolve 10 mg of acid-treated gelatin and 5 mg of TG-S (Ajinomoto) in 1 mL of water. Gelatin nanoparticles were obtained when 1 mL of gelatin solution was injected into 10 mL of ethanol in which 1.7 mg of tocopherol was dissolved using a microsyringe under stirring conditions of an external temperature of 40 ° C. and 800 rpm. Allow to stand for 5 hours at an external temperature of 55 ° C. to enzymatically cross-link gelatin nanoparticles. The average particle size of the above particles was 95 nm as measured using a light scattering photometer and a Microtrack manufactured by Nikiso Corp.

[Evaluation of hair dye composition]
The composition for oxidative hair dye and the composition for hair manicure which were prepared with each following prescription were evaluated.

Hair dyeing method A hair dye having the following formulation was applied to hair [white hair (5 g)] at room temperature and left for 20 minutes. The hair was then rinsed thoroughly with hot water at 40 ° C. and dried at 40 ° C. for 15 minutes (this hair dyeing method is common to all test systems).

(1) Dyeing test: For a hair dye prepared according to the following prescription, dyeing with hair strands (uniformity) and dyeing with a prescription obtained by removing protein nanoparticles from the components of the oxidative hair dye of the prescription The dyeing of each oxidative hair dye was evaluated by comparison with the agent (comparative example). Moreover, visual evaluation was also performed about the gloss of the hair.

Evaluation criteria ○: The example is superior in dyeing properties compared to the comparative example.
(Triangle | delta): The dyeing property of an Example and a comparative example is comparable.
X: The example is inferior to the comparative example.

(2) Shampoo resistance test: About hair dyes prepared according to the following prescription (each example and a comparative example having the above relationship), the hair strands dyed using this were dyed in the following manner. The robustness was compared.
The dyed hair was shampooed three times with a commercially available shampoo (Merit Shampoo; manufactured by Kao Corporation) (40 ° C., 10 minutes), and then dried in a thermostatic bath (40 ° C., 15 minutes). This operation was repeated 10 times, and the color change (fading and discoloration) of the dyed hair was confirmed and evaluated according to the following criteria.

Evaluation criteria ○: The example is superior to the comparative example.
(Triangle | delta): An Example and a comparative example are comparable.
X: The example is inferior to the comparative example.

(3) Hair damage test: For a hair dye prepared according to the following formulation, the surface of the hair before and after dyeing of the hair strand dyed using the same was observed with an electron microscope (magnification 3000 times), and the formulation was oxidized. The degree of damage to the hair cuticles of these hairs was evaluated by comparison with an oxidative hair dye (comparative example) having a formulation in which succinoglycan was removed from the blended ingredients of the hair dye.

Evaluation criteria ○: The example is superior to the comparative example.
(Triangle | delta): An Example and a comparative example are comparable.
X: The example is inferior to the comparative example.

Example 1: Oxidative hair dye (1)
Compounding amount (% by weight)
(First agent)
Paraphenylenediamine 1.0
Propylene glycol 10.0
Sodium edetate 0.3
Sodium sulfite 0.5
Sodium ascorbate 0.5
Casein nanoparticles (Production Example 1) 1.0
Amount of ammonia water pH 10.0 Remaining amount of ion-exchanged water (second agent)
30% hydrogen peroxide solution 6.0
Remaining amount of ion-exchanged water

Example 2: Hair nail polish (2)
Hydroxypropyl cellulose 2 parts by weight Orange 205 1 part by weight Brown 401 1 part by weight Purple 401 1 part by weight Propylene carbonate 8 parts by weight
POE (20) behenyl 0.1 part by weight Phosphoric acid 0.5 part by weight Sodium hydroxide 0.1 part by weight Casein nanoparticles (Production 1) 1 part by weight Ethanol 10 parts by weight Water 73.3 parts by weight

<Production method>
In Example 1, both the first agent and the second agent were prepared by mixing the components. The oxidation hair dye (1) and the hair manicure (2) of Example 2 were subjected to the above (1) dyeing test, (2) shampoo resistance, and (3) hair damage test. The test results are shown in Table 1.

  From the results shown in Table 1, in each example, compared to the conventional product (comparative sample), the fastness of hair dyeing to hair washing is improved, the hair is less damaged, and the hair dyeing property is excellent. I understand that.

Claims (15)

A hair dye composition containing (a) one or more hair dyes or components thereof, and (b) protein nanoparticles having an average particle size of 10 to 200 nm. The hair dye composition according to claim 1, wherein the hair dye is a dye. The hair dye composition according to claim 1, wherein the hair dye is an oxidative hair dye. The hair dye composition according to claim 3, wherein the oxidative hair dye is a combination of an oxidative dye precursor and an oxidant. The hair dye composition according to any one of claims 1 to 4, wherein the content of the protein nanoparticles is 0.01 to 50% by weight based on the weight of the composition. The protein according to any one of claims 1 to 5, wherein the protein is at least one selected from the group consisting of collagen, gelatin, acid-treated gelatin, albumin, ovalbumin, casein, transferrin, globulin, fibroin, fibrin, laminin, fibronectin, or vitronectin. The hair dye composition as described. The hair dye composition according to any one of claims 1 to 6, further comprising 0.1 to 100% by weight of an active ingredient for hair based on the weight of protein. The hair active ingredient is a fragrance, an antibacterial agent, a softener, a moisturizer, an ultraviolet absorber, an active oxygen remover, an antioxidant, a hair restorer, an amino acid, a mineral, or an antimicrobial agent. Hair dye composition. The hair dye composition according to claim 7 or 8, wherein the active hair ingredient is an ionic substance or a fat-soluble substance. The hair dye composition according to any one of claims 1 to 9, wherein the ethanol content is 20% by weight or less. The hair dye composition according to any one of claims 1 to 10, wherein the protein is crosslinked during and / or after the formation of the nanoparticles. The hair dye composition according to claim 11, wherein a crosslinking treatment is performed using an enzyme. The hair dye composition in any one of Claim 1 to 12 containing the casein nanoparticle produced by the following process (a) to (c).
(A) mixing casein with a basic aqueous medium having a pH of 8 or more and less than 11;
(B) adding at least one hair active ingredient to the solution obtained in step (a); and (c) injecting the solution obtained in step (b) into an acidic aqueous medium having a pH of 3.5 to 7.5. : The hair dye composition in any one of Claim 1 to 12 containing the casein nanoparticle produced by the following process (a) to (c).
(A) mixing casein with a basic aqueous medium having a pH of 8 or more and less than 11;
(B) adding at least one hair active ingredient to the solution obtained in step (a); and (c) stirring the solution obtained in step (b) while adjusting the pH of the solution from the isoelectric point. Lowering to pH 1 or more away: A hair dyeing method comprising the step of applying to the hair the hair dye composition according to any one of claims 1 to 14.