KR101954257B1 - Semi-permanent moisturizing treatment composition making hydrophobic surface - Google Patents

Abstract

The present invention relates to a compound capable of forming a strong covalent bond with a specific moiety of hair, skin or fiber to provide a beneficial effect such as damage recovery and prevention of damage, strengthening, water repellency, moisturizing maintenance, Alkoxylated carboxylic acid, alkoxylated (di) amine or alkoxylated (meth) acrylate in the form of a natural or synthetic saturated, unsaturated, branched chain alkoxylated alcohol having two or more carbon atoms in the alkyl moiety having hydrophobicity A compound having a functional group in the terminal of the polyethylene glycol and / or polypropylene glycol moiety existing in the terminal amide compound by substituting an active moiety capable of forming a covalent bond with a residue such as hair, skin or thiol, hydroxyl, carboxyl, Is used. The compound or composition of the present invention can form an outermost hydrophobic layer to maintain proper moisture in hair, skin and fibers, and at the same time, these effects can be persisted semi-permanently.

Description

The present invention relates to a semi-permanent moisturizing treatment composition,

The present invention relates to a composition capable of imparting beneficial functions such as restoration of damage, prevention of damage, strengthening, water repellency, moisturizing, elasticity, and softening to hair, skin or fiber as well as a remarkably improved sustainable effect thereof.

The treatment agents used to improve the surface properties of hair, skin, and fibers to keep them beautiful and healthy can be used for a variety of treatments such as recovery, prevention, strengthening, water repellency, moisturizing, elasticity and flexibility, smoothness, gloss, styling, It is used for the purpose. Recently, various methods for modifying the surface of hair or skin and fibers have been continuously studied. Particularly, in order to improve the sustainability of the effect, in order to overcome the limit of effect persistence due to the effect of ion binding by a conventional counterion or simple physical adsorption, strong covalent bonds with the surface of these substrates are formed, Various studies have been carried out to maintain sustainability for a long time.

Recently, Korean Patent Registration No. 671,935 discloses a composition for hair coating containing polyethylene glycol (PEG) derivatives, wherein polyethylene glycol derivative is covalently bonded to cystine or an amine of hair, Layer to increase the thickness of the entire hair, improve the volume, and transmit the positive characteristics of the polymer to the hair, so that it can be used as a semi-permanent composition for hair coating rather than a one-time use.

Although the above patent provides a moisturizing effect of polyethylene glycol and can increase the thickness and increase the volume through binding, it is present in the outermost one of the A-layer portions of the cuticle which is the outermost layer of healthy natural hair (18-methyl eicosanoic acid) 18-MEA (18-methyl eicosanoic acid), which makes hydrophilic surfaces similar to the characteristics of damaged hair. Therefore, under the humid climatic conditions such as summer, And the disadvantage that the hair sinks and stings and becomes damp. In addition, there is a problem that it is impossible to obtain beneficial properties that can be obtained by hydrophobicity of the surface such as restoration and prevention of damages of hair, skin or fiber, smoothness, gloss, coating effect and the like.

Accordingly, a problem to be solved by the present invention is to provide a composition capable of providing beneficial properties obtained by hydrophobic surface modification such as prevention of damage recovery and damage of hair, skin or fibers, smoothness, glossiness, coating effect and the like. Particularly, a problem to be solved by the present invention is to provide a method for improving the thickness of the entire hair, improving the volume, and providing a characteristic of healthy natural hair by simulating a hydrophobic surface constituting the outermost layer of healthy natural hair, The present invention provides a semi-permanent treatment composition which maximizes the persistency of the skin.

In order to accomplish the above object, the present invention provides a process for producing an alkoxylated alcohol, alkoxylated carboxylic acid, alkoxylated (di) amine or alkoxylated amide represented by the following general formulas (1) to A composition comprising a substance having a reactive moiety capable of forming a covalent bond with a residue such as a thiol, a hydroxyl, a carboxyl, or an amine at the end of a polyethylene glycol or polypropylene glycol to provide.

Wherein R ₁ is hydrogen or a methyl group, m and x are each independently an integer of 2 to 4, and R ₃ is a hydrogen atom or a methyl group, R ₂ is a reactive moiety capable of forming a covalent bond with a thiol, a hydroxyl, a carboxyl or an amine, n is an integer of 1 to 150,000, R ₃ is either hydrogen or a reactive moiety of R ₂ .

In the general formulas (1) to (4), the carbon number of the A moiety to give a hydrophobic group to the outermost surface of the general formulas (1) to (4) is more preferably 6 to 30, and most preferably 10 to 22 carbon atoms.

In the above Chemical Formulas 1 to 4, m and x are more preferably from 10 to 100,000, and still more preferably from 20 to 50,000.

As shown in the above Chemical Formulas 1 to 4, at the ends of such glycol moieties, thiol, hydroxyl, carboxyl, amine and the like exposed on the surface of the hair and the substrate such as skin or fiber With a reactive moiety capable of forming a covalent bond.

In the general formulas (1) to (4), n is an integer of 1 to 150,000, which is one of the main objects of the present invention. The covalent bond with thiol, hydroxyl, carboxyl, amine and the like exposed on the surface of a hair and skin In the aspect, n is preferably 1 to 5,000, more preferably 1 to 500, and most preferably 2 to 100. In this case, it is advantageous to use a reactor as much as possible in order to more efficiently react with reaction residues defined on the hair surface. However, when n is more than 15,000, it is difficult to formulate the product in the product and the film formed by the polymer hardens, Giving an undesirable stiff feel, and the like.

Examples of the reactive moiety (R ₂ ) that can be covalently bonded to the residue of a thiol, hydroxyl, carboxyl, amine, the present invention relates to a process for the preparation of a compound of formula (I) wherein R is selected from the group consisting of carbonate, aldehyde, propionaldehyde, butylaldehyde, nitrophenyl carbonate, aziridine, isocyanate, thiocyanate, but are not limited to, epoxide, tresylate, succinimide, hydroxysuccinimidyl ester, imidazole, oxycarbonylamidazole, imine, thiol thiol, maleimide, vinylsulfone, ethyleneimine, thioether, acrylonitryle, acrylic acid, methacrylic acid ester, but are not limited to, methacrylic esters, crotonic acid or esters thereof, cinnamic acid or its esters, styrene and its derivatives, butadiene, vinyl ether, vinyl ketone, maleic acid ester, vinyl and activated vinyl, carboxylic acid, acetal or hemiacetal, disulfide, aminal or hemiaminal, cyclic carbonate, lactone, thiolactone and azolactone, ketone, (Wherein R represents an alkyl, an aryl group, an aralkyl group, a ring or an unsaturated ring, and X represents I, Br, or Cl), but the present invention is not limited thereto. An example of the reaction of a hair and skin or a protein with a polymer having functional groups of protein residues is illustrated in Schemes 1-12 of Korean Patent No. 671,935, the entire contents of which are incorporated herein by reference.

The present invention is characterized in that a matrix having hydrophobic characteristics is formed on the outermost surface of the substrate by treating the surface of hair and skin or fibers using the above compound capable of forming the fins at the outermost side and polyethylene glycol and / By forming a hydrophilic portion of polypropylene glycol, dehydration of water contained in the hydrophilic portion can be effectively shielded and maintained, and excessive moisture absorption can be prevented. That is, it is possible to provide a semi-permanent treatment composition that provides healthy natural hair characteristics by simulating a hydrophobic surface constituting the outermost layer of healthy natural hair.

That is, the outermost surface of the substrate of the formed reaction has a hydrophobic property, and the adjacent inner side forms a hydrophilic part of polyethylene glycol or polypropylene glycol, thereby forming an effective moisture evaporation shielding film while maintaining the water retaining ability contained in the hydrophilic part It is possible to semi-permanently provide healthy natural hair characteristics by preventing the excessive water loss by acting in the same manner and simulating the hydrophobic surface constituting the outermost layer of healthy natural hair.

For this purpose, the present compounds can be directly used on the surface of a substrate. However, in order to improve the efficiency of reaction and convenience of use, various forms such as powder, tablet, granule, solubilization, dispersion, emulsion, spray, foam, And the like.

In order to formulate the composition according to the present invention, a surfactant, silicone, oil, wax, lower or higher alcohol, fatty acid, alkyl glyceryl ether, ester, saccharide, polymer, powder, animal or plant extract, amino acid, protein, vitamin, , Granules, solubilizing, dispersing, emulsifying, spraying, foaming, gels, and the like, such as preservatives, antioxidants, sequestering agents, whitening agents, perl formers, viscosity adjusting agents, pH adjusting agents, perfumes, dyes, binders and the like , A solution phase, and the like can be additionally used.

The compositions of the present invention can be used in a variety of applications where the reactive moiety forms a strong covalent bond with the hair or skin and the surface of the fiber and forms a hydrophobic moiety on the outermost surface of the reaction substrate, The effect and the moisturizing and maintaining effect are excellent, and at the same time, these effects can be sustained semi-permanently.

FIG. 1 is a graph showing that moisture is evaporated from the hair and the weight is decreased according to the heating time.

Hereinafter, embodiments of the present invention will be described in detail to facilitate understanding of the present invention. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

≪ Preparation of Examples 1-14 and Comparative Examples 1-4 >

20 wt% of each powder or liquid substance was dissolved in 80 wt% of a 50 mM phosphate buffer solution of pH 7 to prepare the compositions of Examples 1 to 14 shown in Table 1 below.

Example 20 wt% 80 wt% One PEG 20 lauryl-hydroxysuccinimidyl ester Phosphate buffer solution (50 mM) 2 PEG 20 lauryl-maleimide Phosphate buffer solution (50 mM) 3 PEG 150 lauryl-hydroxysuccinimidyl ester Phosphate buffer solution (50 mM) 4 PEG 150 lauryl-maleimide Phosphate buffer solution (50 mM) 5 PEG 20 stearyl-hydroxysuccinimidyl ester Phosphate buffer solution (50 mM) 6 PEG 20 stearyl-maleimide Phosphate buffer solution (50 mM) 7 PEG 150 stearyl-hydroxysuccinimidyl ester Phosphate buffer solution (50 mM) 8 PEG 150 Stearyl-maleimide Phosphate buffer solution (50 mM) 9 PEG 20 stearate-hydroxysuccinimidyl ester Phosphate buffer solution (50 mM) 10 PEG 150 stearate-hydroxysuccinimidyl ester Phosphate buffer solution (50 mM) 11 PEG 20 Bifenyl propylenediamine-hydroxy succinimidyl ester Phosphate buffer solution (50 mM) 12 PEG 150 nonenyl propylenediamine-hydroxy succinimidyl ester Phosphate buffer solution (50 mM) 13 PEG 20 Hydrogenated Tallowamide-Hydroxysuccinimidyl Ester Phosphate buffer solution (50 mM) 14 PEG 150 Hydrogenated Tallowamide-Hydroxysuccinimidyl Ester Phosphate buffer solution (50 mM)

The compositions of Comparative Examples 2 to 4 were prepared by dissolving 20 wt% of each powder or liquid substance in 80 wt% of 50 mM phosphate buffer solution of pH 7, and only 50 mM phosphate buffer solution of pH 7 was used as Comparative Example 1.

Comparative Example 1 - 100% by weight of a phosphate buffer solution (50 mM) Comparative Example 2 PEG 20 methyl-hydroxysuccinimidyl ester Phosphate buffer solution (50 mM) 80% Comparative Example 3 PEG 150 methyl-hydroxysuccinimidyl ester Phosphate buffer solution (50 mM) 80% Comparative Example 4 PEG 150 methyl-maleimide Phosphate buffer solution (50 mM) 80%

<Evaluation of moisture content>

A hair tress having a length of 20 cm and a weight of 10 g was prepared and allowed to react for 20 minutes by immersing the composition in a comparative example and an example composition (room temperature 30 ° C) for 3 minutes in a 5% sodium lauroyl sulfate solution. Thereafter, the shampoo was cleaned by hand rubbing for 30 seconds while massaging with bubbling and washing in running water at 30 DEG C for 3 minutes. The water was removed from the towel and allowed to stand in a constant temperature and humidity room at 25 ° C and 55% relative humidity for 12 hours. Then, in order to confirm whether there is a covalent bonding effect with the surface of the hair, it was immersed in a solution of 5% sodium lauroyl sulfate for 3 minutes and then massaged for 30 seconds by hand rubbing and bubbling. After washing the shampoo for 5 minutes, the shampoo was washed, and the hair was removed from the towel. The hair was washed 5 times in a constant temperature and humidity room at 25 ° C and 55% relative humidity for 12 hours. The primary evaporation humidity, which is an indicator of the amount of water absorbed on the surface of the hair, was measured using a weight measured at 38 minutes by heating the sample at a temperature of 50 degrees Celsius for 40 minutes using an HR83-P model measuring meter of METLLER Co., The secondary evaporation humidity, which is an index of bound moisture in the inside of the hair by heating at 180 ° C. for 30 minutes, was measured using the weight measured at 68 minutes as an index thereof. Document indicates using the values of A, B, C to each of the primary and secondary moisturizing rate (%) on calculated using Equations (1) and (2) and the results are shown in Table 3 below.

[Equation 1]

Primary moisturizing rate (%) = ((Primary initial weight A - Primary initial weight B) / Primary initial weight A) X 100

&Quot; (2) &quot;

Second moisturizing rate (%) = ((Secondary initial weight B - Secondary weight C) / Second initial weight B) X 100

Primary moisturizing rate Secondary moisturizing rate Primary initial weight A Primary weight B First Moisture Ratio (%) Secondary initial weight B Secondary weight C Second Moisture Ratio (%) Example 1 100.0 88.6 11.40 88.6 85.1 3.95 Example 2 100.0 88.7 11.30 88.7 85.3 3.83 Example 3 100.0 85.3 14.70 85.3 81.2 4.81 Example 4 100.0 85.5 14.50 85.5 81.6 4.56 Example 5 100.0 89.4 10.60 89.4 85.7 4.14 Example 6 100.0 89.5 10.50 89.5 85.7 4.25 Example 7 100.0 85.9 14.10 85.9 81.7 4.89 Example 8 100.0 85.9 14.10 85.9 81.6 5.01 Example 9 100.0 89.6 10.40 89.6 85.9 4.13 Example 10 100.0 85.8 14.20 85.8 81.6 4.90 Example 11 100.0 90.1 9.90 90.1 86.2 4.33 Example 12 100.0 87.1 12.90 87.1 82.7 5.05 Example 13 100.0 88.1 11.90 88.1 84.6 3.97 Example 14 100.0 85.8 14.20 85.8 81.5 5.01 Comparative Example 1 100.0 91.5 8.50 91.5 90.1 1.53 Comparative Example 2 100.0 90.3 9.70 90.3 88.4 2.10 Comparative Example 3 100.0 89.2 10.80 89.2 86.8 2.69 Comparative Example 4 100.0 89.5 10.50 89.5 87.0 2.79

As shown in the above Table 3, it is preferred that the composition contains an alkoxylated alcohol, an alkoxylated carboxylic acid, an alkoxylated (di) amine and an alkoxylated amide having 12 to 22 carbon atoms whose alkyl moiety has a hydrophobic group The case of Examples 1 to 14 containing a hydroxy-succinimidyl ester which is a structure forming a covalent bond with the amine residue at the hair surface on the polyethylene glycol moiety and a maleimide derivative which is a structure forming a covalent bond with the thiol residue is simply Comparative Example 1 in which phosphoric acid buffer solution was treated and a hydroxysuccinimidyl ester and a thiol residue which are structures that form a covalent bond with an amine residue on the surface of hair on the terminal of the alkoxylated alcohol portion having an alkyl moiety of 1 carbon atom Compared with Comparative Examples 2 to 4 having a maleimide derivative which is a structure forming a covalent bond, the second moisturizing rate (%) is very high Respectively. This reflects the fact that when the hydrophobicity of the alkyl moiety is lower than that of the alkyl moiety in the water adsorbed on the surface, the bonding water bound to the polyethylene glycol moiety largely evaporates when the first moisturizing property is evaluated. In contrast, In the case of 1 to 14, the second moisturizing rate (%) shows a relatively larger value than the comparative example because of the hydrophobic surface characteristics of the covalently bonded substances on the surface of the hair, As shown in Fig.

<Evaluation of effect persistence>

The effect of covalent bonding on the compositions of Comparative Examples 1 to 4 and Examples 1 to 14 was confirmed. The hair tress used in the measurement of the moisture resistance was immersed in a 5% sodium lauroyl sulfate solution for 3 minutes, then hand rubbed by hand for 30 seconds, massaged while bubbling, washed for 3 minutes in running water at 30 degrees Celsius, , And the shampoo simulation process in which the shampoo was allowed to stand in a constant temperature and humidity room at 25 ° C and 55% relative humidity for 12 hours was repeated seven times. Then, the hair tress was cut to a length of 1 cm, and 500 mg of the hair was heated for 40 minutes at a temperature of 50 ° C using a measuring instrument of a HR83-P model of METLLER Co. to measure the moisture absorbed by the hair. Min, and the secondary evaporation humidity, which is the index of the bound moisture in the hair heated at 180 ° C. for 30 minutes, was measured using the weight measured at 68 minutes, and the index was measured Using the values of A, B, and C shown in FIG. 1, the first and second moisturizing rates (%) after seven washes were calculated using Equations 1 and 2, and the results are shown in Table 4 below.

Primary moisturizing rate Secondary moisturizing rate Primary initial weight A Primary weight B First Moisture Ratio (%) Secondary initial weight B Secondary weight C Second Moisture Ratio (%) Example 1 100 89.1 10.9 89.1 85.7 3.82 Example 2 100 89.0 11.0 89.0 85.5 3.93 Example 3 100 86.0 14.0 86.0 82.3 4.30 Example 4 100 86.1 13.9 86.1 82.3 4.41 Example 5 100 89.9 10.1 89.9 86.1 4.23 Example 6 100 89.8 10.2 89.8 86.2 4.01 Example 7 100 86.5 13.5 86.5 82.5 4.62 Example 8 100 86.4 13.6 86.4 82.5 4.51 Example 9 100 90.0 10.0 90.0 86.5 3.89 Example 10 100 86.1 13.9 86.1 82.0 4.76 Example 11 100 90.6 9.4 90.6 87.1 3.86 Example 12 100 87.6 12.4 87.6 83.5 4.68 Example 13 100 88.5 11.5 88.5 85.3 3.62 Example 14 100 86.0 14.0 86.0 82.0 4.65 Comparative Example 1 100 91.3 8.7 91.3 89.8 1.64 Comparative Example 2 100 91.5 8.5 91.5 89.2 2.51 Comparative Example 3 100 91.3 8.7 91.3 89.0 2.52 Comparative Example 4 100 91.2 8.8 91.2 88.8 2.63

As shown in Table 4, in the evaluation results of the moisturizing and maintaining effect after 7 rinses, the composition was also evaluated in the same manner as in Example 1, Hydroxy-succinimidyl ester which is a structure forming a covalent bond with an amine residue on the surface of hair at the terminal of the polyethylene glycol moiety of the (meth) acrylated or alkoxylated amide, and a structure which forms a covalent bond with the thiol residue In the case of Examples 1 to 14 containing a mid derivative, Comparative Example 1 in which a phosphoric acid buffer solution was treated and a covalent bond with an amine residue on the surface of the hair at the terminal of the alkoxylated alcohol portion having an alkyl portion of 1 carbon atom Which is a structure forming a covalent bond with hydroxysuccinimidyl ester and thiol residue, (%) Of the poly (ethylene glycol) was evaluated to be very superior to that of Comparative Examples 2 to 4 having a derivative. In the case of water adsorbed on the polyethylene glycol surface, when the number of carbon atoms in the alkyl moiety is small, In the case of Examples 1 to 14, the secondary moisturizing rate (%) is relatively larger than that in the comparative example. In contrast, in the case of Examples 1 to 14, the secondary moisturizing rate (% It is a phenomenon that occurs by maintaining the moisture even at the temperature of the evaluation condition of the first humidification property due to the hydrophobic surface property of the substances covalently bonded to the surface, and even after cleaning up to 7 times, strong bonding due to covalent bonding with the surface of the hair is maintained As shown in Fig.

Claims (6)

A cosmetic composition for skin moisturizing and elasticity characterized by containing at least one of compounds represented by the following formulas (1) to (4)
&Lt; Formula 1 >

(2)

(3)

&Lt; Formula 4 >

Wherein R ₁ is hydrogen or a methyl group, m and x are each independently an integer of 2 to 4, and R ₃ is a hydrogen atom or a methyl group, R ₂ is a reactive moiety capable of forming a covalent bond with the thiol or amine of the skin and is an aldehyde, propionaldehyde, butylaldehyde, nitrophenyl carbonate but not limited to, nitrophenyl carbonate, isocyanate, epoxide, tresylate, hydroxysuccinimidyl ester, oxycarbonylimidazole, thiol, maleimide, (maleimide) and vinylsulfone, n is an integer of 1 to 150,000, R ₃ is hydrogen or a reactive residue of R ₂ . The cosmetic composition for skin moisturizing and elasticity according to claim 1, wherein the carbon atom number of A is 6 to 30. The cosmetic composition for skin moisturizing and elasticity according to claim 1, wherein m and x are independently an integer of 10 to 100,000. delete A hair treatment composition characterized by containing at least one of compounds represented by the following formulas (1) to (4):
&Lt; Formula 1 >

(2)

(3)

&Lt; Formula 4 >

Wherein R ₁ is hydrogen or a methyl group, m and x are each independently an integer of 2 to 4, and R ₃ is a hydrogen atom or a methyl group, R ₂ is a reactive moiety capable of forming a covalent bond with the thiol or amine of the hair and is an aldehyde, propionaldehyde, butylaldehyde, nitrophenyl carbonate but not limited to, nitrophenyl carbonate, isocyanate, epoxide, tresylate, hydroxysuccinimidyl ester, oxycarbonylimidazole, thiol, maleimide, maleimide and vinylsulfone, n is an integer from 1 to 150,000, R ₃ is hydrogen or a reactive residue of R ₂ , . A composition for prevention of fiber damage, water repellency, moisturizing and softening, which comprises at least one of compounds represented by the following formulas (1) to (4)
&Lt; Formula 1 >

(2)

(3)

&Lt; Formula 4 >

Wherein R ₁ is hydrogen or a methyl group, m and x are each independently an integer of 2 to 4, and R ₃ is a hydrogen atom or a methyl group, R ₂ is a reactive moiety capable of forming a covalent bond with the thiol or amine of the fiber and is selected from the group consisting of aldehyde, propionaldehyde, butylaldehyde, but not limited to, nitrophenyl carbonate, isocyanate, epoxide, tresylate, hydroxysuccinimidyl ester, oxycarbonylimidazole, thiol, maleimide, maleimide and vinylsulfone, n is an integer from 1 to 150,000, R ₃ is hydrogen or a reactive residue of R ₂ , .

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