KR20170055774A

KR20170055774A - Composition for surface modification

Info

Publication number: KR20170055774A
Application number: KR1020150158976A
Authority: KR
Inventors: 김시원; 김동완; 김경환; 손성길; 이정래; 이상민
Original assignee: 주식회사 엘지생활건강
Priority date: 2015-11-12
Filing date: 2015-11-12
Publication date: 2017-05-22
Also published as: KR101773678B1

Abstract

The composition for surface modification according to the present invention may contain at least one functional group capable of covalently bonding to existing surface modifying components with protein residues of hair, skin or fibers; And a reactive surface modifying component having at least one specific functional group at the same time in the same molecule, thereby forming a covalent bond without damaging hair, skin or fiber, and significantly improving the effect through lamination, thereby providing a desired surface modification effect semi-permanently .

Description

[Composition for surface modification]

The present invention relates to a composition for surface modification of hair, skin or fibers.

In general, a person's haircuticle consists of flatly superimposed cells (scales). Cuticle cells are attached from the root to the tip of the hair as if they were roof tiles. Each cuticle layer has a thickness of about 0.3 to 0.5 mu m, and a portion of the cuticle shown is about 5 to 10 mu m. Cuticles of human hair are generally stacked five to ten layers. Each cuticle cell in the hair is composed of various sublamella layers such as an epicuticle, an A-layer, an exocuticle, an endocuticle, and an inner layer, and a cell membrane (Cell membrane complex). The outermost epicuticle layer is covered with covalently bound lipid (fatty acid), and the most abundant component is 18-Methyl Eicosanoic Acid (18-MEA). This layer constitutes the outer β-layer of the cuticle cell membrane complex and acts like lubrication, friction reduction, and hydrophobic surface formation.

In the hair, the portion that goes out from the scalp is called the morning sock, which varies with the lifespan and length of the hair. Also, it varies depending on environmental stress such as dryness, ultraviolet rays, seawater, and limestone of a swimming pool when using hair, shampoo, hair dryer, brushing, perm, hair color. In particular, the morpheme surrounding the outer part of the moraine is damaged if it is accumulated in a complex manner even if it is not directly affected by such stress. Damaged hair is peeled off or partially peeled off from the tip of the mosquito. These hairs lose their gloss and become non-smooth due to diffuse reflection of light. More damage to the hair leads to the complete removal of the layer of mosquito, which exposes the inner follicle and eventually breaks or breaks the hair.

Various treatments have been attempted to improve the surface of hair damaged by 18-MEA. In particular, a product that provides a hair surface modifying effect, that is, a hair strengthening effect, such as hair manicure or hair essence, Have been sold or are being applied through hairdressing rooms. Especially, there have been many products such as shampoos for strengthening the hair through coating of the hair surface or penetration of amino acids into the hair.

However, in the case of using the hair-modifying ingredient as the hair-modifying ingredient, it only provides a temporary and short-term effect until the next washing after the treatment, but there is always the inconvenience of reprocessing after cleaning.

The same kind of amino acid residues are exposed to the keratin of the hair, the collagen of the skin, the wool or the silk material, so that the same mechanism as the hair can be applied to the skin or the fiber in addition to the hair.

Accordingly, Patent Document 1 discloses a non-aqueous personal care product for skin or hair, which comprises a non-water-based functional group capable of forming a covalent bond with the hair or the protein residues on the skin surface, such as carbonate, aldehyde, propionaldehyde ), Butylaldehyde, nitrophenyl carbonate, aziridine, isocyanate, thiocyanate, epoxide, tresylate, succinimide, maleic anhydride, succinimide, maleimide, hydroxysuccinimidyl ester, imidazole, oxycarbonylamidazole, imine, thiol, vinylsulfone, , Ethyleneimine, thioether, acrylonitrile, acrylic acid or methacrylic acid ester (acrylic acid or methacrylic acid) wherein R is any one selected from the group consisting of alkyl, aryl, aralkyl, cyclic and unsaturated rings, X is I, Br or Cl, ) And a hair surface modifying component having at least one member selected from the group consisting of a non-water-based part and a water-based part, and the mixture is used immediately before use , Lysine, which is harmful to the human body or contains a small amount of amino acids of hair proteins (1.9 to 3.1%) and skin keratin (3.1 to 6.9%) in the case of the above-mentioned various functional groups, Or keratin (2.3 ~ 3.8%), which is about 16.6 ~ 18% of the hair and the skin, One, there is a problem that must be synthesized separately.

Korean Patent Publication No. 2008-0064467

It is an object of the present invention to provide a composition for surface modification capable of continuously imparting a semi-permanent surface modifying effect without damaging hair, skin or fibers.

As means for solving the above problems,

At least one functional group capable of covalently bonding to the surface modifying component with amino acid residues of hair, skin or fiber surface proteins; And at least one functional group selected from the group consisting of sulfo-hydroxysuccinimide ester, n-hydroxysuccinimide ester, pyridyl disulfide, thiol, haloacetyl, amine, carbonate, maleimide and hydroxy; The reactive surface modifying component

And a surface modifying composition.

As another means for solving the above problems,

Skin, or fiber care products comprising said surface modifying composition.

As another means for solving the above problems,

And covalently bonding the hair, skin or fiber surface with the surface modification composition to form a modified layer.

The composition for surface modification according to the present invention contains a functional group capable of covalently bonding with proteins of hair, skin or fiber and a reactive surface modifying component having two or more specific functional groups to form a covalent bond without damaging hair, skin or fibers It provides semi-permanent surface modification effect.

The present invention relates to a cosmetic composition comprising at least one functional group capable of covalently bonding to a surface modifying component with amino acid residues of hair, skin or fiber surface proteins; And a reactive surface modifying component having at least one specific functional group at the same time in the same molecule.

The "composition for surface modification" may comprise a hair surface modifying composition, a skin surface modifying composition and / or a fiber surface modifying composition.

In the present invention, the term 'hair surface modification' refers to a modification of the surface of the hair by coating the hair or bonding effective materials to make the hair look thicker or to give a conditioning effect such as luster, softness, calmness or smoothness It imparts beneficial properties to make the hair beautify, increase the attractiveness, change the appearance, give moisturizing power to the hair, or block the ultraviolet rays and apply it to the hair to keep the hair healthy, It can be used in a similar way to others. The effect of modifying the surface of the hair can be exhibited, for example, the improvement of the tensile strength of the hair and the increase of the thickness of the hair.

In the present invention, the term 'skin surface modification' refers to modification of the surface of the skin by coating the skin or bonding effective materials to change the properties of the surface of the skin to brighten the skin, or to provide a conditioning effect such as glossiness, softness, To increase skin's attractiveness, to change appearance, to moisturize the skin, to block ultraviolet rays, and to apply it to the skin in order to keep the skin healthy. Can be used in a similar manner. The skin surface modifying effect can exhibit, for example, the effect of improving the wrinkles of the skin and increasing the skin moisturizing power.

In the present invention, the term 'fiber surface modification' refers to modification of the surface of a fiber by coating fibers such as wool or silk or bonding effective materials to prevent damage to the fiber, increase persistence of perfume, bleaching, sterilization, By imparting beneficial properties such as softening of the fibers, they can be applied to the fibers, dispersed, or otherwise used in a similar manner to keep the fibers fresh. The effect of modifying the surface of the fiber can exhibit effects such as, for example, an increase in fiber flexibility and an increase in retention of fiber color.

The surface modifying component may be selected from the group consisting of conventional antioxidant, conditioning, shine, gloss, moisturizing, whitening, ultraviolet shielding, incense, wrinkle preventing, hair volume, dandruff itching improvement, wool hair growth, acne care, The present invention relates to a substance having the efficacy of a skin care, an atopic care, a dyeing or a bio-bonding, and specifically a natural extract, an amino acid, a peptide, a protein, a polymer, a silicone, a fatty alcohol, a fatty acid, a wax, And may be any component capable of modifying the surface of hair, skin or fibers.

Examples of the natural product-derived extracts include Rhodiola extract, Camellia sinensis extract, Ursol acid, Rhododendron extract, Seaweed extract, Sunflower seed extract, Gossam extract, Ginseng extract, Rhodiola extract, Marigold extract, Birch sap, Birch tree extract, Extracts, bergamot extracts, honey extracts, cassis extracts, pomegranate extracts, lemon extracts, extracts of green tea, green tea extracts, bergamot extract, The protein and the peptide may be selected from the group consisting of silk, silk, polylysine, seaweed, wool, hair, and the like, such as a broccoli extract, a honey extract, a cranberry extract, a berry extract, Proteins and peptides obtained from wheat, and the like.

Examples of the amino acid include glycine, alanine, valine, leucine, isoleucine, threonine, serine, cysteine, cystine, methionine, aspartic acid, asparagine, glutamic acid, diiodothyrosine, lysine, arginine, histidine, phenylalanine, tyrosine, tryptophan, Proline, and the like.

The peptide may include peptides composed of 2 to 200 amino acids, and the protein may include keratin, collagen, gelatin, and plant proteins or hydrolysates of these proteins. The keratin is preferably hydrolyzed keratin, and more preferably has a molecular weight of 200 to 150,000 Da.

The polymer may be a linear polymer network compound having a molecular weight of 1,000 to 1,000,000 or a branched polymer network compound and may have a double bond or a ring structure if they contain a variety of substituents it may also be used, within the molecule terminal to any one -COONa to facilitate the reaction for attaching a reactive functional group in _{vivo, -COOK, -COOH, -NH 2,} -NHR, -NR 2, -Cl , -Br, -I, or -F group, it is preferable to include at least one reactive moiety in the molecule. And more preferably it is 10,000 to 500,000 degree chain and branched-chain polymer molecule, yet the terminal either to -COONa, -COOK to facilitate the reaction for attaching a reactive functional group in vivo, -COOH, -NH _2, of the carbon- NHR, -NR ₂ , -Cl, -Br, -I, or -F group may be used as the compound having at least one reactive moiety in the molecule. For example, an amino acid polymer such as polylysine, a polyamine polymer, a polycarboxylic acid polymer, a methacryloylethyl betaine / methacrylate copolymer, an octyl acrylamide / acrylate / methacrylate copolymer as a polymer, Amphoteric polymers such as octylacrylamide / acrylates / butylaminoethyl methacrylate copolymers or polyvinylpyrrolidone, PVP / VA copolymers, PVP / dimethyl (meth) acrylate copolymers (PVP / Dimethylaminoethylmethacrylate Copolymer), non-ionic polymers such as polyurethane, acrylate methacrylate copolymer, Vie / crotonate / vinyl neodecanoate copolymer VA / Crotonates / Vinyl Neodecanoate Copolymer) and the like But is not limited thereto.

Examples of the silicone oils include dimethicone, trimethicone, phenyltrimethicone, amodimethicone, amodimiphenyltrimethicone, amodi-pentaphenyltrimethicone, dimethylpolysiloxane, methylphenylpolysiloxane, decamethyl But are not limited to, cyclopentasiloxane, methyltrimethicone, phenyltrimethicone, mechicone, cyclomethicone, alkylmethylsiloxane, dimethicone polyol, trimethylsilylamodimethicone.

The fatty alcohols are preferably chain and branched fatty alcohol compounds having about 10 to 50 carbon atoms, such as lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol and behenyl alcohol, But is not limited thereto.

The fatty acids are preferably chain and branched fatty acid compounds having about 10 to 50 carbon atoms such as 18-methylecycanoic acid, lauric acid (dodecanoic acid), stearic acid and isostearic acid. It is not limited. The fatty acid derivatives include, but are not limited to, propionic acid and the like.

The waxes may be, for example, but not limited to, candelilla wax, carnauba wax, rice wax, beeswax, lanolin, ozokerite, ceresin wax, paraffin wax, microcrystalline wax, polyethylene wax .

The ester oil may be selected from, for example, isopropyl myristate, butyl myristate, isopropyl palmitate, ethyl stearate isopropyl rinolate, decyl myristate, cetyl myristate, cetyl palmitate, hydrogenated polyisobutene Hydrogenated polyisobutaine, and the like.

In the present invention, the functional groups capable of forming a covalent bond with proteins on the surface of the hair include amine, imidoester, aryl azide, diazirine, hydroxymethylphosphine, pentafluorophenyl ester, pyridyl disulfide, sulfo- But are not limited to, amides, esters, amides, amides, amides, amides, amides, amides, amides, One selected from the group consisting of hydroxysuccinimidyl ester, imidazole, oxycarbonylamidazole, imine, thiol, vinyl sulfone, ethyleneimine, thioether, acrylonitrile, acrylic acid or methacrylic acid ester, disulfide and ketone Or more.

The amino acid residue of the protein may also be a reactive residue of a thiol, a hydroxyl, a carboxyl or an amine.

Wherein the reactive surface modifying component comprises at least one functional group capable of covalently bonding to the surface modifying component with a protein on the surface of hair, skin or fiber; And at least one functional group selected from the group consisting of sulfo-hydroxysuccinimide ester, n-hydroxysuccinimide ester, pyridyl disulfide, thiol, haloacetyl, amine, carbonate, maleimide and hydroxy; It is preferable to have them at the same time.

In one embodiment of the reactive functional group of the present invention, the functional group reactive with the carboxyl group of glutamic acid or aspartic acid among the amino acids of the keratin protein existing on the hair surface is an amine, And functional groups capable of reacting with the amine group of lysine include carboxyl, N-hydroxysuccinimide ester, sulfo-hydroxysuccinimide ester, sulfo-NHS ester, imidoester and aryl azide. The functional groups reactive with the thiol of cysteine are maleimide, haloacetyl, Hydrazide, and pyridyl disulfide. In addition, the functional group reactive with the hydroxyl group of serine, threonine, and tyrosine includes, but is not limited to, isocyanate.

In one embodiment of the reactive surface modifying component, the 12-mercaptododecanoic acid NHS ester, 3- (2-pyridyldithio) propylonyl hydrazide (3- (2- pyridyldithio) propionyl hydrazide, N- (4- [p-azidosalicylamido] butyl) -3 '- (2'-pyridyldithio) propionamide 3'- (2'-pyridyldithio) propionamide, 4- (p-azidosalicylamido) -butylamine, bis (sulfosuccinimidyl) glutarate-d0 Bis (sulfosuccinimidyl) glutarate-d0), bis (sulfosuccinimidyl) 2,2,4,4-glutarate-d4, bis Bis (sulfosuccinimidyl) suberate, bis (sulfosuccinimidyl) suberate-d0), bis (sulfosuccinimidyl) Bis (sulfosuccinimidyl) 2,2,7,7-suberate-d4), bis (NHS) PEO ₅ (Bis (NHS) PEO ₅ ), bis HS) PEO ₉ (bis (NHS) PEO ₉ ), bis (2- [succinimidoxycarbonyloxy] ethyl) sulfone, C6- succinimidyl 4-hydrazone Succinimidyl 4-formylbenzoate, 1,4-di- (3 '- [2 ' -pyridazine (3'- [2'yridyldithio] propionamido) butane), disuccinimidyl glutarate, ditiobis (succinimidyl propionate Dithiobis (succimidylpropionate), Disuccinimidyl substrate, Disuccinimidyl tartarate, 3,3'-dithiobis (sulfosuccinimidyl propionate (3) , 3'-Dithiobis (sulfosuccinimidylpropionate)), ethylene glycol bis (succinimidylsuccinate), succinimidyl 4- (N- (N-maleimidomethyl) cyclohexane-1-carboxy- (6-amidocaproate), quinmimidyl 6- (3 '- [2 Succinimidyl 6- (3 '- [2-pyridyl-dithio] propionamido) hexanoate, succinimidyl 4-hydrazinone is succinimidyl 4- hydrazinonicotinate acetone hydrazine, N-succinimidyl 6- (4'-azide-2'-nitrophenylamino) hexanoate, N Succinimidyl (4-iodoacetyl) aminobenzoate, succinimidyl-6- (? -Maleimidopropionamido) aminobenzoate, (3-maleimidopropionamido) hexanoate, 4-succinimidyloxycarbonylmethyl-? - (2-pyridyldithio) toluene, N- succinimidyloxycarbonylmethyl- (2-pyridyldithio Succinimidyl 3- (2-pyridyldithio) propionate, ethylene glycol bis (sulfo-succinimidyl succinate), sulfosuccinimidyl succinate (6 - Methyl -? - [2-pyridyldithio) toloamido] hexanoate), sulfosuccinimidyl 6- (3 ', 5'- - [2-pyridyl-dithio] propionamido) hexanoate, sulfosuccinimidyl 6- (3 '- [2-pyridyl- (4-iodo-acetyl) aminobenzoate, sulfosuccinimidyl 4- (N-maleimido-methyl) cyclohexane-1-carboxylate (Sulfosuccinimidyl 4- (1-carboxylate), sulfosuccinimidyl 4- (p-maleimidophenyl) butyrate and TSAT (succimidylaminotricetate) (Trifunctional) Or two or more can be, but is not limited thereto.

The reactive surface modifying component may be used in an amount of 0.001 to 50 parts by weight, 0.001 to 30 parts by weight, 0.01 to 10 parts by weight, or 0.1 to 5 parts by weight based on 100 parts by weight of the total composition. If the content is less than 0.001 part by weight, there is a limit to the effect of the active ingredient. If the content is more than 50 parts by weight, there is a problem in stability of the formulation and the stability with time of the formulation.

As an embodiment of the composition for surface modification according to the present invention,

The amino acid of the keratin protein existing in excess on the hair surface reacts first with the reactive hair surface modifying component (first reactive surface modifying component), and one or more functional groups capable of bonding with the remaining functional groups after the first reaction and one And the second reactive surface modifying component simultaneously containing the functional groups, so that bio-bonding can be continuously performed, and the components can be sequentially stacked on the surface of the hair. Therefore, it is preferable that the component to be bound to the living body includes two or more reactive functional groups in the molecule when laminated through a continuous bioconjugation reaction.

The term "laminate" refers to a method in which hair is reacted with at least one functional group capable of reacting with the amino acid on the hair surface as a first reactive surface modifying component, and a surface modifying component containing at least one of the functional groups and reacted with the first reactive surface modifying component (Second reactive surface modifying component) comprising at least one functional group capable of reacting with the remaining functional group and a functional group covalently bonding with the protein is repeated to obtain the first reactive surface modifying component and the second reactive surface modifying component Reactive surface modifying component are alternately reacted and laminated to form a modified layer. In actual use, when alternately using a shampoo comprising a first reactive surface modifying component and a rinse comprising a second reactive surface modifying component, the first reactive surface modifying component and the second reactive surface modifying component are alternately stacked Whereby a modified layer having a multilayer structure can be formed. Although only the hair mechanism has been described above, since the same mechanism can be applied to skin or fiber, the composition for surface modification of the present invention can be used for skin or fiber.

If necessary, an effective component that imparts a final efficacy is further coupled by continuously reacting the active component containing at least one functional group capable of covalently bonding to the protein on the outermost layer of the laminated multilayered modified layer, In addition to the surface modification effect, additional effects can be given. The efficacy components are antioxidant, conditioning, shine, gloss, moisturizing, whitening, sunscreen, incense, anti wrinkle, hair volume, dandruff itching improvement, wool hair growth, acne care, textile care, oral care, body odor prevention, But is not limited to, a component having the efficacy of a cure, dye, microcapsule, nanocapsule, micro needle, needle patch, inclusion or bio junction.

In order to increase the effect of the surface modifying composition according to the present invention, fatty acid such as palmitic acid and stearic acid, fatty alcohol, cation such as long chain alkyl quaternary ammonium salt of straight chain and branched chain When mixed with a cationic polymer such as a cationic surfactant, cationized cellulose, cationic guar, cationized polyvinylpyrrolidone, silicone, etc., formulation can be facilitated. In order to formulate cosmetics such as solvents, surfactants, thickeners, stabilizers, preservatives, coloring agents, pH adjusters, metal ion sequestering agents, coloring agents, pearlizing agents, external appearance improvers, pigments and powder particles, Components may be incidentally included. The ingredients for the formulation may be used in an amount of 40 to 99 parts by weight based on 100 parts by weight of the total composition.

The composition for surface modification according to the present invention can be used for the preparation of a hair, skin or fiber surface modification care product.

For hair, use it for hair such as a pre-shampoo composition, shampoo, rinse treatment, wax, spray, mousse, hair lotion, essence, hair cream, permanent hair dye, temporary hair dye, Cosmetic preparations which can be used for skin such as skin, lotion, essence, serum, cream, gel, foundation, powder, make-up base and point make-up can all be included in the skin The fibers may also include fiber care agents that can be used for fibers such as fabric softener, fiber dye, laundry detergent, and partial treatment agent.

In one embodiment of a hair care product comprising a surface modifying composition according to the present invention, the shampoo composition comprises a 12-mercapto-dodecanone NHS ester and the rinse composition comprises 3- (2-pyridyldithio) propyl When neil hydrazide is included, repeated use of shampoo rinse results in the addition of compound 12-mercaptododecanoic acid NHS ester and 3- (2-pyridyldithio) propionyl hydrazide to the hair surface protein amino acid Amide bonds, and disulfide bonds, it is possible to maximize the hair surface modifying effect.

More preferably, the composition for surface modification according to the invention contains a reactive surface modifying component, and when the activity of the formulation is lowered in the aqueous system, it is easier to maintain its activity in the non-aqueous formulation, it may be mixed with a buffer for pH control, or the reaction may be performed by contacting with water in the washing process. Examples of non-aqueous formulations include liquid, sheet, powder, tablet, oil, wax, ampoule, gel and the like which are used as ordinary non-aqueous cosmetic preparations. In addition, a method of blocking a derivative in which a functional group having a reactive function and a component having a function of a hair surface modifying component are combined through the encapsulation from moisture may also be used.

In order to increase the effect of the reactive surface modifying component in the composition for surface modification according to the present invention, a mixture of 2-basic acid esters such as dioctyl succinate, dioctyl adipate, diethyl sebacate and the like, polyol, polyethylene glycol, propylene glycol, Hexylene glycol, butanediol, and isomers thereof, glycerol, benzyl alcohol, ethoxydiglycol and derivatives thereof. The above-mentioned solvents increase the permeability of hair and skin, and are used as a solvent of a poorly soluble substance. More preferably, the solvent used to increase the activity maintaining effect of the reactive surface modifying component is diethyl sebacate, ethoxy glycol, bis-ethoxy glycol cyclohexane 1,4-dicarboxylate, and the like.

In addition,

Covalently bonding hair, skin or fiber surfaces with the surface modifying composition to form a modified layer

To a method of modifying hair, skin or fiber surfaces.

In one embodiment,

Forming a first modified layer by binding an amide bond, a thioether bond or a disulfide bond to the hair, skin or fiber surface with the surface modifying composition; And

Amide bonding to the surface modifying composition on the first modified layer. A thioether bond or a disulfide bond to form a second modified layer;

To provide a method for modifying hair, skin or fiber surfaces.

Further, the surface modification method of the present invention may include a step of alternately laminating the first modified layer and the second modified layer at least once to form a modified layer having a multilayer structure.

In addition, the surface modification method of the present invention may further include a step of finishing the lamination using an efficacious component having a functional group capable of covalently bonding to proteins on hair, skin, or fiber surface.

The amide bond may be a bond formed by the reaction of NHS or sulfo-NHS with an amine, but is not limited thereto. The amide bond is preferably reacted at a pH of from 2 to 10, more preferably at a pH of from 6 to 10, and most preferably from a neutral to weakly alkaline aqueous solution of about pH 7-9 And is particularly preferable.

The disulfide bond may be a bond formed by reaction of pyridyl disulfide and thiol, but is not limited thereto. The disulfide bond is preferably reacted at a pH of from 2 to 10, more preferably at a pH of from 5 to 9, and most preferably at a pH of from about 6.5 to about 7.5, desirable.

The thioether bond may be a bond formed by the reaction of haloacetyl and thiol or a bond formed by the reaction between maleimide and thiol, but the present invention is not limited thereto. The thioether bond formed by the reaction of haloacetyl with thiol is preferably reacted at a pH of 4 to 14, more preferably at a pH of 6.0 to 10.0, It is particularly preferable that the reaction is carried out in a neutral to slightly alkaline aqueous solution of about 7.0 to 9.0, since the reaction efficiency can be increased most. The thioether bond formed by the reaction of maleimide with thiol is preferably reacted at a pH of 2-10, more preferably at a pH of 5-9, more preferably at a pH of 6.5 -7.5 in the neutral aqueous solution is particularly preferable because the reaction efficiency can be maximized.

The bond formation reaction is completed within a period of from 1 minute to 30 minutes.

In one embodiment of the composition for surface modification according to the present invention, a first reactive surface modifying component comprising an NHS ester (N-hydroxysuccinimide ester) and thiol in the same molecule is reacted with a hair surface to form hair Amines and NHS esters present in surface proteins form amide bonds. The second reactive surface modifying component comprising an amine and a pyridyl disulfide is reacted in the same molecule by a two-step reaction, and the thiol of the surface-modified component bonded to the surface of the remaining hair after the first- A disulfide bond is formed between the pyridyl disulfide. Thereafter, by reacting the first reactive surface modifying component containing the NHS ester and the chiols in the same molecule, the amide bond is formed by reacting with the amine exposed at the end of the second step reaction product, and the remaining functional group A disulfide bond is formed by reacting a second reactive surface modifying component having both a pyridyl disulfide capable of reacting with a thiol and an amine. By continuously reacting the reactive surface modifying component containing two or more functional groups in the same molecule, the reactive surface modifying component forms a covalent bond on the hair surface and laminated to form a continuous multi-layered modified layer, The surface modification effect can be maximized.

In the reaction, the amide bond, which reacts with NHS or sulfo-NHS and amine, is preferably reacted at pH 2-10, more preferably at pH 6-10, neutral to weak It is particularly preferable to carry out the reaction in an alkaline aqueous solution since the reaction efficiency can be maximized. The disulfide bond reacted with pyridyl disulfide and thiol is preferably reacted at pH 2-10, more preferably at pH 5-9, neutral at pH 6.5-7.5, It is particularly preferable that the reaction is carried out in an aqueous solution since the reaction efficiency can be maximized. The thioether bond, in which haloacetyl reacts with thiol, is preferably reacted at a pH of 4 to 14, more preferably at a pH of 6.0 to 10.0, and more preferably at a pH of 7.0 to 9.0 By weight in a neutral to slightly alkaline aqueous solution is particularly preferable because the reaction efficiency can be increased most. The thioether bond formed by the reaction of maleimide and thiol is preferably reacted at a pH of 2-10, more preferably at a pH of 5-9, more preferably at a pH of 6.5- It is particularly preferable that the reaction is carried out in a neutral aqueous solution at about 7.5, since the reaction efficiency can be maximized. All reactions are completed within a minute to within 30 minutes.

In one embodiment of the present invention, a first reactive surface modifying component simultaneously comprising an NHS ester and a thiol is reacted with a lysine containing an amine of a hair surface keratin protein to form an amide bond Subsequently, the reaction of forming a disulfide bond by reacting with a second reactive surface modifying component having pyridyl disulfide and amine at the same time was shown as first and second reactions. The tertiary and quaternary reactions showed the reaction to form a multi-layered modified layer through amide bonds and disulfide bonds in the same manner as the first and second reactions.

The following Reaction Scheme 1 is only a part of the reforming reaction of the multi-layered structure, and the reaction can proceed continuously.

[Reaction Scheme 1]

The reactive surface modifying component combined with the hair does not fall off well during the general washing due to shampoo, detergent, soap, etc., and can be kept almost permanently attached to the hair.

As described above, the present invention relates to a process for producing a multilayer structure by reacting a surface modifying component having two or more reactive functional groups on the surface of hair, skin or fibers to form a multilayered multilayer, Can be increased. In addition, an effect component having a functional group capable of covalently bonding to proteins on the surface of hair, skin, or fiber can be additionally formed at the outermost portion of the modified layer, thereby providing an additional effect in addition to the surface modification effect.

Hereinafter, the present invention will be described in detail by the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

Example 1 to 6 and Comparative Example 1 to 6

The hair surface modifying compositions of Examples 1 to 6 and Comparative Examples 1 to 6 were prepared by the compositions and contents shown in the following Tables 1 and 2, and the resulting composition was treated with hair, and the tensile strength and thickness of the hair were measured As an example of hair surface modifying effect, hair strengthening effect and hair thickening effect were confirmed.

The test hair supplier Burelex's normal hair was treated for 20 minutes with one agent containing thioglycolic acid, treated with a solution containing hydrogen peroxide, left for 10 minutes, and washed with shampoo. To produce damaged hair.

In order to eliminate the influence of the active ingredient adsorbed on the hair and to confirm the effect of the combined ingredients, the hair was washed once with a 15% solution of surfactant SLES (Sodium Lauryl Ether Sulfate), and the tensile strength and the thickness of the hair , And the measurement results of Examples 1 to 6 and Comparative Examples 1 to 6 showed an average value of the results of measurement of 100 hair strands.

The tensile strength of normal hair before damage and damaged hair after damage was measured using a hair tension tensile strength tester (Diastron Generic Tensil Tester) at a clamping distance of 20 mm and a tensile speed of 20 mm / min.

The tensile strength of the normal hair is a value obtained by averaging the tensile strength of 50 brux normal hair measured at each test, and the tensile strength of the perm hair was measured by the above method using the tensile strength The tensile strength of the treated hair was measured by treating each sample on 50 strands of damaged hair, and the rate of increase of the tensile strength relative to the damaged hair was calculated.

The hair length / short axis length before and after treatment was measured using a hair cross section measuring apparatus (Laser Scan Micrometer, Mitutoyo LSM 3100) after the normal hair before damage and the damaged hair after damage was measured, Respectively.

[Equation 1]

Cross-sectional area (m ² ) =

The average increase / decrease ratio of the cross-sectional area before and after the processing converted to Equation (1) was calculated by the following equation (2).

&Quot; (2) "

Cross-sectional average increase / decrease rate (%) =

division
(weight%) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Distilled water 48.0 48.0 48.0 48.0 48.0 48.0 12-mercaptododecanoic acid NHS ester - - - - - - 3- (2-pyridyldithio) -propionyl hydrazide (3- (2-pyridyldithio)
propionyl hydrazide) - - - - - - 12-Mercaptododecanoic acid 1.0 1.0 1.0 1.0 1.0 1.0 3- (2-pyridyldithio) -propionic acid 1.0 1.0 1.0 1.0 1.0 1.0 The buffer (pH 7) 50.0 50.0 50.0 50.0 50.0 50.0 Sum 100.0 100.0 100.0 100.0 100.0 100.0 Number of processing 1 time 5 times 10 times 1 time 5 times 10 times

division
(weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Distilled water 48.0 48.0 48.0 48.0 48.0 48.0 12-Mercaptododecanoic acid NHS ester
(First reactive surface modifying component) 1.0 1.0 1.0 1.0 1.0 1.0 3- (2-pyridyldithio) -propionyl hydrazide
(Second reactive surface modifying component) 1.0 1.0 1.0 1.0 1.0 1.0 12-Mercaptododecanoic acid - - - - - - 3- (2-pyridyldithio) -propionic acid - - - - - - The buffer (pH 7) 50.0 50.0 50.0 50.0 50.0 50.0 Sum 100.0 100.0 100.0 100.0 100.0 100.0 Number of processing 1 time 5 times 10 times 1 time 5 times 10 times

Compared to Comparative Examples 1 to 3 in which the hair surface modifying components of Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to one or repeated treatment of the hair surface modifying component containing one or less reactive functional groups (Table 3) In the case of Examples 1 to 3 in which the hair surface modifying component containing two or more hair surface modifying components was once or repeatedly treated was remarkably increased in tensile strength and excellent in the hair surface modifying effect.

division Of normal hair
Tensile strength value (gmf) The tensile strength value of the damaged hair (gmf) Tensile strength value after treatment (gmf) Tensile Strength Increase Rate (%) Comparative Example 1 47.94 45.43 45.55 0.26 Comparative Example 2 48.12 46.03 46.17 0.30 Comparative Example 3 48.54 45.98 46.12 0.30 Example 1 48.97 46.72 49.85 6.70 Example 2 47.83 46.99 53.37 13.58 Example 3 48.09 45.96 55.96 21.76

Compared with the results of the hair thickness measurement (Examples 4 to 6 and Comparative Examples 4 to 6) (Table 4) and Comparative Examples 4 to 6 in which the hair surface modifying component containing one or less reactive functional groups was subjected to the once or repeated treatment, the reactive functional groups In the case where the hair surface modifying component containing two or more hair surface modifying components was once or repeatedly treated, the hair cross-sectional area was significantly increased in Examples 4 to 6, and the effect of increasing hair thickness, that is, hair surface modifying effect, was evaluated to be excellent.

division Of normal hair
The hair cross section (僚 m ² ) The hair cross-sectional area of the damaged hair (ν m ² ) The hair cross-sectional area (νm ² ) Increase rate of hair cross-sectional area (%) Comparative Example 4 4042.56 3642.89 3649.82 0.19 Comparative Example 5 3912.08 3648.23 3652.09 0.11 Comparative Example 6 3998.42 3709.73 3717.76 0.22 Example 4 4013.37 3731.63 3856.69 3.35 Example 5 3897.68 3618.88 3923.37 8.41 Example 6 3937.84 3680.70 4213.09 14.46

Formulation example : Hair surface For reforming hair Product manufacturing

1) Manufacture of hair shampoo comprising first reactive surface modifying component

Hair shampoos were prepared according to the ingredients of the following Table 5 according to the conventional method for producing hair products.

Compounding ingredient weight (%) Polyquaternium 0.5 Sodium lauryl sulfate (30%) 20.0 Sodium polyoxyethylene lauryl sulfate 30.0 Coconut oil fatty acid diethanolamide 3.0 Quaternary ammonium cationic surfactant 2.0 Carbopol-1342 0.3 Paraoxybenzoic acid ester 0.2 12-Mercaptododecanoic acid NHS ester
(First reactive hair surface modifying component) 0.5 antiseptic Suitable amount Spices Suitable amount The buffer (pH 7.0) Balance Sum 100.0

2) Preparation of a hair rinse containing a second reactive surface modifying component

The hair rinse was prepared according to the conventional hair product manufacturing method with the ingredients and contents shown in Table 6 below.

Compounding ingredient weight (%) Dicetyldimethylammonium chloride (68%) 3.3 Stearamido dimethylamine 2.0 Propylene glycol 0.5 Citric acid 0.1 Cetyl alcohol 2.0 Stearyl alcohol / Cetearyl-20 1.0 Cyclomethicone 3.25 3- (2-pyridyldithio) -propionyl hydrazide
(Second reactive hair surface modifying component) 0.5 antiseptic Suitable amount Spices Suitable amount The buffer (pH 7.0) Balance Sum 100.0

Claims

At least one functional group capable of covalently bonding to the surface modifying component with amino acid residues of hair, skin or fiber surface proteins; And at least one functional group selected from the group consisting of sulfo-hydroxysuccinimide ester, n-hydroxysuccinimide ester, pyridyl disulfide, thiol, haloacetyl, amine, carbonate, maleimide and hydroxy; The reactive surface modifying component
And the surface modifying composition.

The method according to claim 1,
Wherein the surface modifying component is at least one selected from the group consisting of natural extracts, amino acids, peptides, proteins, polymers, silicones, fatty alcohols, fatty acids, waxes, ester oils and derivatives thereof.

The method according to claim 1,
The functional groups capable of covalently bonding to the amino acid residues of the hair, skin or fiber surface proteins include amine, imidoester, aryl azide, diazirine, hydroxymethylphosphine, pentafluorophenyl ester, pyridyl disulfide, sulfo-hydroxy The present invention relates to a process for the preparation of a compound of the formula I wherein R 1 is selected from the group consisting of succinimidyl esters, alkoxylamines, hydrazides, haloacetyls, azides, carbonates, maleimides, aldehydes, propionaldehyde, butylaldehyde, nitrophenylcarbonates, aziridines, isocyanates, thiocyanates, epoxides, , Succinimide, hydroxysuccinimidyl ester, imidazole, oxycarbonylamidazole, imine, chiol, vinylsulfone, ethyleneimine, thioether, acrylonitrile, acrylic acid or methacrylic acid ester, disulfide and ketone Wherein the composition is at least one selected from the group consisting of:

The method according to claim 1,
Wherein the amino acid residue of the protein is thiol, hydroxyl, carboxyl or amine.

The method according to claim 1,
The reactive surface modification component may be 12-mercaptododecanoic acid NHS ester, 3- (2-pyridyldithio) propionyl hydrazide, 3 '- (2' -Pyridyldithio) propionamide (N- (4- [p-Azidosalicylamido] butyl) (p-azidosalicylamido) -butylamine, bis (sulfosuccinimidyl) glutarate- d0), bis (sulfosuccinimidyl) 2,2,4,4-glutarate-d4, bis (sulfosuccinimidyl) Bis (sulfosuccinimidyl) suberate-d0), bis (sulfosuccinimidyl) suberate, bis (sulfosuccinimidyl) suberate d2, 2,2,7,7- bis (sulfosuccinimidyl) suberate-2,2,7,7-d4), bis _{(NHS) PEO 5 (bis (} NHS) PEO 5), bis _{(NHS) PEO 9 (bis (} NHS) PEO 9), Bis (2- [succinimidoxycarbonyloxy] ethyl) sulfone, and C6-succinimidyl 4-hydrazone are used as C6-Succinimidyl 4-hydrazinonicotinate acetone hydrazine, C6-Succinimidyl 4-formylbenzoate, 1,4-di- (3 '- [2'pyridyldithio] propionamido) Di- (3 '- [2'yridyldithio] propionamido) butane, disuccinimidyl glutarate, dithiobis (succimidylpropionate) Disuccinimidyl substrate, disuccinimidyl tartarate, 3,3'-dithiobis (3,3'-dithiobis (sulfosuccinimidylpropionate)), ethylene glycol bis (Ethyleneglycol bis (succinimidylsuccinate)), succinimidyl 4- (N-maleimidomethyl) cyclo (N-maleimidomethyl) cyclohexane-1-carboxy- (6-amidocaproate), quinmimidyl 6- (3 '- [2-pyridyl- Succinimidyl 6- (3 '- [2-pyridyl-dithio] propionamido) hexanoate, succinimidyl 4-hydrazinone is succinimidyl 4-hydrazinonicotinate acetone hydrazine, N-succinimidyl 6- (4'-azide-2'-nitrophenylamino) hexanoate), N-succinimidyl Succinimidyl (4-iodoacetyl) aminobenzoate, succinimidyl-6- (β-maleimidopropionamido) aminobenzoate, N-succinimidyl ) hexanoate, 4-succinimidyloxycarbonylmethyl-? - (2-pyridyldithio) toluene, N-succinimidyl 3- (2-pyridyl) Yl) propionate (N-Su (2-pyridyldithio) propionate, ethylene glycol bis (sulfo-succinimidylsuccinate), sulfosuccinimidyl 6 - (? - methyl-? - [2- (2-pyridyldithio) toluamido] hexanoate), sulfosuccinimidyl 6- (3 '- [2-pyridyl- (3'- [2-pyridyl-dithio] propionamido) hexanoate), sulfosuccinimidyl (4'-iodo-acetyl) aminobenzoate -iodo-acetyl) aminobenzoate, sulfosuccinimidyl 4- (N-maleimido-methyl) cyclohexane-1-carboxylate, sulfosuccinimidyl 4- At least one selected from the group consisting of neuramidyl 4- (p-maleimidophenyl) butyrate and TSAT (succimidylaminotricetate) (Trifunctional) Composition.

The method according to claim 1,
The reactive surface modification component
The surface modifying component may have both the thiol and the NHS ester in the same molecule at the same time,
Wherein the surface modifying component simultaneously contains an amine and a pyridyl disulfide in the same molecule.

The method according to claim 1,
Wherein the reactive surface modifying component comprises 0.001 to 50 parts by weight based on 100 parts by weight of the total composition.

The method according to claim 1,
Antioxidant, conditioning, shine, shine, moisturizing, whitening, sunscreen, incense, anti wrinkle, hair volume, dandruff itch improvement, wool hair tonic, acne care, textile care, oral care, body odor prevention, nail care, Or bio conjugation.

A care product comprising the surface modifying composition of claim 1.

Covalently bonding a hair, skin or fiber surface with the surface modifying composition of claim 1 to form a modified layer
Of the hair, skin or fiber surface.

11. The method of claim 10,
Linking a hair, skin or fiber surface with an amide bond, thioether bond or disulfide bond to the surface modifying composition of claim 1 to form a first modified layer; And
Forming an amide bond, thioether bond or disulfide bond on the first modified layer by the surface modification composition of claim 1 to form a second modified layer;
Of the hair, skin or fiber surface.

12. The method of claim 11,
Wherein the step of laminating the first reforming layer and the second reforming layer is carried out one or more times to form a modified layer of a multilayered structure.

12. The method of claim 11,
Further comprising the step of finishing the lamination using an efficacious component having a functional group capable of covalently binding to the hair, skin, or protein on the surface of the fiber.

14. The method of claim 13,
The efficacy components are antioxidant, conditioning, shine, gloss, moisturizing, whitening, sunscreen, incense, anti wrinkle, hair volume, dandruff itching improvement, wool hair growth, acne care, textile care, oral care, body odor prevention, Care, dyeing or bio-bonding.