KR100356676B1 - Lyotropic liquid crystalline compound and a method for preparation thereof, and cosmetic composition containing thereof - Google Patents

Abstract

The present invention relates to a concentration-transition liquid crystal crystalline compound represented by the following general formula (I), a preparation method thereof, and a cosmetic composition containing the same.

(I)

In the above formula,

n is an integer between 0 and 60,

A is -CH _2- , -CHCH _3- ,

D ¹ and D ² are the same as or different from each other, and are hydrogen or an alkyl group containing C ₁ to C ₃₁ straight or branched chain, saturated or unsaturated, with or without a hydroxyl group,

R is a substituent having the following structure. :

Wherein B is a methyl group at the 5, 7 or 8 position of tocopherol,

m is 1 to 3,

D is -CH ₂ -CH (CH ₃ )-or -CH = C (CH ₃ )-.)

The concentration transition type liquid crystal forming compound of the present invention forms a stable liquid crystal when applied to the skin to continuously supply moisture to the skin and at the same time can be used for the recovery and prevention of the skin damaged by the external environment, and gradually releases tocopherol to the biofilm As a material that can prevent the aging of the skin, there is no irritation to the skin, and when the active substance is introduced into the liquid crystal, a stable supply of the active substance is possible.

Description

Lyotropic liquid crystalline compound and a method for preparation, and cosmetic composition containing thereof}

The present invention relates to a novel lyotropic liquid crystalline compound represented by the following general formula (I), a preparation method thereof, and a cosmetic composition containing the same.

[Formula 1]

(I)

In the above formula,

n is an integer between 0 and 60,

A is -CH _2- , -CHCH _3- ,

D ¹ and D ² are the same as or different from each other, and are hydrogen or an alkyl group containing C ₁ to C ₃₁ straight or branched chain, saturated or unsaturated, with or without a hydroxyl group,

R is a substituent having the following structure. :

Wherein B is a methyl group at the 5, 7 or 8 position of tocopherol,

m is 1 to 3,

D is -CH ₂ -CH (CH ₃ )-or -CH = C (CH ₃ )-.)

The liquid crystal structure is thermodynamically stable as an intermediate form between solid and liquid, and its properties can be divided into temperature dependent liquid crystals and concentration transition liquid crystals according to concentrations and temperatures. It is a state. However, the stratum corneum, the outermost structure of the skin, is composed of keratinocytes and intercellular keratinocytes surrounding it.The keratinocyte lipid is a lamellar liquid crystal structure that strengthens keratinocytes to protect the skin from external damage and loss of water in vivo. From the fact that it has a function of preventing and keeping the surface of the skin smooth, in cosmetics and pharmaceuticals, liquid crystals similar to biological lamellae are used to impart moisturizing, suppleness, and barrier functions to the skin, or use them to deliver active ingredients, There is an increasing interest in liquid crystals such as stabilization.

Accordingly, the present inventors also studied liquid crystal forming compounds to use liquid crystals in the cosmetic field, and as one of the studies, the molecular structure of the concentration transfer type liquid crystal forming compounds conventionally used to provide a concentration transfer type liquid crystal forming compound by synthesis. The structural characteristics of the concentration-transformed liquid crystal-forming compound were found to be at least one long-chain alkyl group or at least one hydrophilic group having an unsaturated alkyl group and a cationic, anionic or neutral group. In other words, the structural characteristics of the liquid crystal forming compound is focused on the hydrophilic part capable of hydrogen bonding and the minor part consisting of a long-chain alkyl group. In addition, the hydrophobic group of the concentration-transformed liquid crystal forming compounds that have been conventionally used has been designed in consideration of its excellent liquid crystal forming ability when having two parallel alkyl groups rather than one alkyl group. In addition, the concentration transition type liquid crystal forming compound by the synthesis should be safe for the skin, stable liquid crystal when applied to the skin to supply water continuously, and have the property to introduce the active ingredient into the liquid crystal.

In view of the above-described points in molecular design, the inventors of the present invention have excellent solubility in solvents, excellent affinity to the skin, and form stable liquid crystals on the surface of the skin, compared to existing concentration-transformed liquid crystal forming compounds. In order to stabilize the liquid crystal structure, polyalkylene glycol was introduced as a neutral hydrophilic group between two parallel alkyl groups, and the present invention was completed by introducing a tocopheryl group into the molecular structure as a factor controlling the liquid crystal formation ability.

Accordingly, it is an object of the present invention to provide a concentration transition type liquid crystal forming compound represented by general formula (I).

Another object of the present invention is to provide a method for preparing a concentration-transition liquid crystal forming compound (I).

Further, another object of the present invention is to provide a cosmetic composition containing the concentration transition type liquid crystal forming compound (I).

1 is a photograph taken with a polarizing microscope of the cosmetic formulation of Formulation Example 1 according to the present invention (× 500).

According to the present invention, a novel concentration transition type liquid crystal forming compound represented by the following general formula (I) is provided.

[Formula 1]

(I)

In the above formula,

n is an integer between 0 and 60,

A is -CH _2- , -CHCH _3- ,

D ¹ and D ² are the same as or different from each other, and are hydrogen or an alkyl group containing C ₁ to C ₃₁ straight or branched chain, saturated or unsaturated, with or without a hydroxyl group,

R is a substituent having the following structure. :

Wherein B is a methyl group at the 5, 7 or 8 position of tocopherol,

m is 1 to 3,

D is -CH ₂ -CH (CH ₃ )-or -CH = C (CH ₃ )-.)

The method for producing a concentration-transition liquid crystal forming compound wherein D ¹ and D ^{2, which} are the substituents of the general formula (I), provided in the present invention is represented by hydrogen,

(1-1) mixing the O, O'-bis (2-aminopropyl) polyalkylene glycol with an alkali or organic base and tocopheryl succinic acid and reacting to prepare a diamide compound:

(1-2) step of dissolving the diamide compound prepared in step (1-1) in an organic solvent, followed by filtration to remove insoluble matters and recrystallization:

Characterized in that it comprises a.

In addition, the substituents D ¹ and D ² of the above-described general formula (I) provided in the present invention are the same as or different from each other, and C ₁ to C ₃₁ straight or branched chain, saturated or unsaturated, containing or not containing hydroxyl groups. Method for producing a concentration-transition liquid crystal forming compound represented by an alkyl group,

(2-1) O, O'-bis (2-aminopropyl) polyalkylene glycol is dissolved in dichloromethane or ethanol, and then reacted with a C ₁ to C ₃₁ halo alkyl group or an epoxy compound under an inert air stream to give a general formula ( Obtaining intermediates of II):

(II)

(Wherein D ³ and D ⁴ are the same as or different from each other, and C ₁ to C ₃₁ are linear or branched, saturated or unsaturated, alkyl groups containing or not containing hydroxyl groups, n and A are general formulas (I As defined in)):

(2-2) a step of preparing a diamide compound by mixing an alkali or organic base with an intermediate of formula (II) obtained in step (2-1) and tocopheryl succinic acid chloride and then reacting: and

(2-3) step of dissolving the diamide compound prepared in step (2-2) in an organic solvent, followed by filtration to remove insoluble matters and recrystallization:

Characterized in that it comprises a.

In the above-mentioned manufacturing method, the unit of polyalkylene glycol in O, O'-bis (2-aminopropyl) polyalkylene glycol in steps (1-1) and (2-1) is suitably 1 to 60. The alkylene is preferably ethylene or propylene. Suitable halo alkyl compounds are C ₁ to C ₃₁ straight or branched chain, saturated or unsaturated, alkyl groups containing or without hydroxyl groups, and epoxy compounds include epichlorohydrin, epibromohydrin, 3,4- Epoxy-1-chlorobutane, 3,4-epoxy-1-bromobutane, 4,5-epoxy-1-chloropentane, 4,5-epoxy-1-bromopentane, 2,3-epoxy-1- Hydropropane is suitable.

In addition, as the alkali in the steps (1-1) and (2-2), potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, magnesium oxide, potassium oxide, and the like may be used, and triethylamine, di Amines, such as isopropylethylamine and pyridine, are suitable. Tocopheryl chloride succinic acid is natural or synthetic and reacts tocopheryl succinic acid obtained by reacting tocopherol having a form of α-, β-, δ-, γ-, ε- and succinic anhydride with a chloride such as thionyl chloride. To be prepared.

Examples of the organic solvent in (1-2) and (2-3) include alcohol solvents such as methanol, ethanol, propanol and isopropanol; Halogen solvents such as dichloromethane, chloroform, 1,2-dichloroethane and carbon tetrachloride; And hydrocarbon solvents such as n-hexane, cyclohexane, benzene and toluene; Ester solvents such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate.

The above manufacturing method can be summarized by the following Reaction Scheme 1, for example, of the concentration transition type liquid crystal forming compound of the present invention.

The concentration-transfer type liquid crystal forming compound of formula (I) prepared by the above-mentioned manufacturing method forms a stable liquid crystal when applied to the skin to supply moisture to the skin and gradually releases tocopherol, thereby preventing the aging of the biofilm. As a substance having no irritation to the skin and introducing an effective substance for the recovery and prevention of the skin into the liquid crystal, it is stable to the skin and can be supplied continuously, which is excellent in preventing the skin's elasticity and preventing skin aging. The effect can be provided.

On the other hand, the cosmetic composition of the present invention is to form a stable liquid crystal by containing the above-described concentration transition liquid crystal forming compound in an amount of 0.001 to 30% by weight, preferably 0.1 to 20% by weight relative to the total weight of the composition. It was confirmed that, due to this liquid crystal structure it was confirmed that the moisturizing, softening effect is increased.

The cosmetic composition of the present invention is not particularly limited in its formulation, and may have, for example, a formulation such as supple cosmetic water, nourishing cosmetic water, massage cream or nourishing cream.

In addition, components other than the concentration-transition liquid crystal compound constituting the cosmetic composition of the present invention can be appropriately selected and blended by those skilled in the art according to the dosage form and the desired effect without difficulty.

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, and Test Examples, but the present invention is not limited to these examples.

Production Example 1 Preparation of α-tocopheryl succinic acid

10 g of dl-α-tocopherol was placed in a 500 ml round bottom flask and dissolved in 200 ml of acetone. 2.79 g of succinic anhydride and 2.8 g of triethylamine were added thereto at 30 ° C, and stirred for 4 hours at the same temperature. After completion of the reaction, the residue was concentrated and dissolved in ethyl acetate, and then the organic layer was washed twice with dilute hydrochloric acid solution and three times with water, and the organic layer was separated and dried. After concentration under reduced pressure, petroleum ether was added and left overnight. The resulting solid was filtered and dried to give 10 g (yield = 80%) of α-tocopherylsuccinic acid.

Preparation Example 2 Preparation of δ-Tocopherol Succinic Acid

8.66 g (yield = 75%) of δ-tocopherylsuccinic acid was obtained in the same manner as in Reference Example 1, except that 10 g of δ-tocopherol and 2.98 g of succinic anhydride were used.

Preparation Example 3 Preparation of γ-Tocopherol Succinic Acid

8.91 g (yield = 72%) of g-tocopherylsuccinic acid was obtained in the same manner as in Reference Example 1, except that 10 g of γ-tocopherol and 2.88 g of succinic anhydride were used.

Preparation Example 4 Preparation of Chloride α-Tocopheryl Succinic Acid

1.34 g of dimethylformamide and 2.18 g of thionyl chloride were mixed and stirred well for 30 minutes, and a solution of 9.27 g of α-tocopheryl succinic acid of Preparation Example 1 was added dropwise to 20 ml of tetrahydrofuran, and then, at room temperature, 2 After stirring for a time, α-tocopherylsuccinoyl chloride was prepared.

Preparation Example 5 Preparation of N, N'-bis (2,3-dihydroxypropyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 500

250 ml of dichloromethane is placed in a 500 ml round bottom flask under argon stream, and 60.0 g (0.1 mole) of O, O'-bis (2-aminopropyl) polyethylene glycol 500 (molecular weight about 600) is mixed well. While stirring vigorously, 14.6 mL (Fw 74.08, d = 1.1170, 2.2 equivalents) of glycidol was slowly added over 1 hour while maintaining the temperature at about 30 ° C to 50 ° C. The reaction was further carried out for about 10 hours, and after cooling to room temperature, the solvent was dried under reduced pressure. N, N'-bis (2,3-dihydroxypropyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 500 52 g (yield = 70%) were obtained.

[Manufacture example 6]

N, N'-bis (2) was prepared in the same manner as in Preparation Example 5, except that 90.0 g (0.1 mole) of O, O'-bis (2-aminopropyl) polyethylene glycol 800 (molecular weight: about 900) was used. 68 g (yield = 65%) of (3-dihydroxypropyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 800 were obtained.

[Manufacture example 7]

Except for using 100.0 g (0.05 mole) of O, O'-bis (2-aminopropyl) polyethylene glycol 1900 (molecular weight approx. 2000) and 7.3 ml of glycidol (Fw 74.08, d = 1.1170, 2.2 equiv) 67.6 g (yield = 63%) of N, N'-bis (2,3-dihydroxypropyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 1900 was obtained in the same manner as in Preparation Example 5. Got it.

[Manufacture example 8]

Except for using 23.0 g (0.1 mole) of O, O'-bis (2-aminopropyl) polypropylene glycol 130 (molecular weight: about 230), N, N'-bis ( 13020.8 g (yield = 55%) of 2,3-dihydroxypropyl) -O, O'-bis (2-aminopropyl) polypropylene glycol was obtained.

[Manufacture example 9]

Except for using 40.0 g (0.1 mole) of O, O'-bis (2-aminopropyl) polypropylene glycol 300 (molecular weight: about 400), N, N'-bis ( 33.4 g (yield = 61%) of 2,3-dihydroxypropyl) -O, O'-bis (2-aminopropyl) polypropylene glycol 300 were obtained.

Example 1 N, N'-bis (α-tocopherylsuccinoyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 500

To the 500 ml round flask, 1.67 g of magnesium oxide and 10 g of water were added, followed by stirring. After mixing, 5 g of O, O'-bis (2-aminopropyl) polyethylene glycol 500 (molecular weight: about 600) was added thereto and 40 ml of tetrahydrofuran. Add. The chloride α-tocopheryl succinic acid prepared in Preparation Example 4 was added dropwise over 1 hour with vigorous stirring at room temperature. Stir for another 2 hours, filter and wash the solid on the filter with 200 ml of chloroform. Combine the filtrate and the tax solution, separate the water layer, and dry and concentrate the organic layer. N, N'-bis (α-tocopherylsuccinoyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 500 9.46 g ( Yield = 70%) was obtained, the analysis results are shown in Table 1 below.

Example 2

7.5 g (0.01 mole) of N, N'-bis (2,3-dihydroxypropyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 500 prepared in Preparation Example 5 and Instead of 9.27 g of α-tocopheryl succinic acid of Preparation Example 1, 11.13 g (2.1 equivalents) of α-tocopheryl succinic acid was added dropwise over 1 hour, stirred for another 2 hours, and filtered. The solid on the filter is then washed with 200 ml of chloroform. After combining the filtrate and the tax solution, the water layer is separated and the organic layer is dried and concentrated to form N, N'-bis (2,3-dihydroxypropyl) -N, N'-bis (α-tocopherylsuccinoyl) -O. 12.9 g of (O'-bis (2-aminopropyl) polyethylene glycol 500 (yield = 73%)) was obtained, and the analysis results are shown in Table 1 below.

Example 3

Δ-tocopherylsuccnic acid instead of 6.0 g (0.01 mole) of O, O'-bis (2-aminopropyl) polyethylene glycol 500 and 9.27 g of α-tocopheryl succinic acid of Preparation Example 1 in Preparation Example 4 N, N'-bis (δ-tocopherylsuccinoyl) -O, O was carried out in the same manner as in Example 1 except for using δ-tocopherylsuccinic chloride prepared using 10.5 g (2.1 equivalents). 10.6 g (yield = 68%) of '-bis (2-aminopropyl) polyethylene glycol 500 was obtained, and the analysis results are shown in Table 1 below.

Example 4

7.5 g (0.01 mole) of N, N'-bis (2,3-dihydroxypropyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 500 prepared in Preparation Example 5 and prepared in Preparation Example 4 Instead of 9.27 g of α-tocopheryl succinic acid of Example 1, 10.5 g (2.1 equivalents) of δ-tocopherylsuccnic acid prepared using 10.5 g (2.1 equivalents) of δ-tocopheryl succinic acid was used. Except for N, N'-bis (2,3-dihydroxypropyl) -N, N'-bis (δ-tocopherylsuccinoyl) -O, O'-bis, except that 11.1 g (yield 65%) of (2-aminopropyl) polyethylene glycol 500 was obtained, and the analysis results are shown in Table 1 below.

Example 5

Prepared using 6.17 g (2.1 equivalents) of α-tocopheryl succinic acid instead of 5.0 g of O, O'-bis (2-aminopropyl) polyethylene glycol 800 and 9.27 g of α-tocopheryl succinic acid of Preparation Example 1 in Preparation Example 4. N, N'-bis (α-tocopherylsuccinoyl) -O, O'-bis (2-aminopropyl) was prepared in the same manner as in Example 1 except that the prepared chloride α-tocopherylsuccinic acid was used. Polyethylene glycol 800 5.49g (71% yield) was obtained, the analysis is shown in Table 1 below.

Example 6

1,0.5 g (0.01 mole) of N, N'-bis (2,3-dihydroxypropyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 800 prepared in Preparation Example 6 and prepared in Preparation Example 4 In the same manner as in Example 2 except for using the α-tocopheryl succinic acid chloride prepared using 11.13 g (2.1 equivalents) of α-tocopheryl succinic acid instead of 9.27 g of α-tocopheryl succinic acid of Example 1. N, N'-bis (2,3-dihydroxypropyl) -N, N'-bis (α-tocopherylsuccinoyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 800 14.3 g ( Yield = 69%) was obtained, the analysis results are shown in Table 1 below.

Example 7

Prepared using 2.78 g (2.1 equivalents) of α-tocopheryl succinic acid instead of 5 g of O, O'-bis (2-aminopropyl) polyethylene glycol 1900 and 9.27 g of α-tocopheryl succinic acid of Preparation Example 1 in Preparation Example 4 N, N'-bis (α-tocopherylsuccinoyl) -O, O'-bis (2-aminopropyl) polyethylene was carried out in the same manner as in Example 1 except that the chloride α-tocopherylsuccinic acid was used. Glycol 1900 3.5g (yield = 70%) was obtained, and the analysis results are shown in Table 1 below.

Example 8

1,0.0 g (0.005 mole) of N, N'-bis (2,3-dihydroxypropyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 1900 prepared in Preparation Example 7 and Preparation Example 4 The same procedure as in Example 2 was carried out except that α-tocopherylsuccinic acid chloride prepared using 5.57 g (2.1 equivalents) of α-tocopheryl succinic acid was used instead of 9.27 g of α-tocopheryl succinic acid of Example 1. N, N'-bis (2,3-dihydroxypropyl) -N, N'-bis (α-tocopherylsuccinoyl) -O, O'-bis (2-aminopropyl) polyethylene glycol 2000 9.1 g ( Yield = 60%) was obtained, the analysis results are shown in Table 1 below.

Example 9

Instead of 4.6 g of O, O'-bis (2-aminopropyl) polypropylene glycol 130 and 9.27 g of α-tocopheryl succinic acid of Preparation Example 1 in Preparation Example 4, 22.26 g (2.1 equivalents) of α-tocopheryl succinic acid was used. N, N'-bis (α-tocopherylsuccinoyl) -O, O'-bis (2-aminopropyl was carried out in the same manner as in Example 1 except for using the prepared α-tocopherylsuccinic acid chloride. Polypropylene glycol 130 14.8g (yield = 59%) was obtained, the analysis results are shown in Table 1 below.

Example 10

Instead of 4.0 g of O, O'-bis (2-aminopropyl) polypropylene glycol and 9.27 g of α-tocopheryl succinic acid of Preparation Example 1 in Preparation Example 4, 11.13 g (2.1 equivalents) of α-tocopheryl succinic acid was used. N, N'-bis (α-tocopherylsuccinoyl) -O, O'-bis (2-aminopropyl was carried out in the same manner as in Example 1 except for using the prepared α-tocopherylsuccinic acid chloride. Polypropylene glycol 300 10.4g (73% yield) was obtained, the analysis results are shown in Table 1 below.

compound ¹ H-NMR (δ, ppm) IR (cm ^-1 , C = O) ¹³ C-NMR (ppm, C = O) Example 1 0.85 (12H, t), 1.14-1.50 (27H, m), 1.85 (2H, m), 1.96 (3H, s), 2.04 (3H, s), 2.07 (3H, s), 2.57 (2H, t) , 2.85 (2H, t), 2.95 (2H, t), 3.45 (4H, m), 3.61 (20H, t), 4,01 (2H, m) 16351101 171 Example 2 0.84 (12H, t), 1.15-1.50 (27H, m), 1.83 (2H, m), 1.95 (3H, s), 2.04 (3H, s), 2.08 (3H, s), 2.55 (2H, t) , 2.85 (2H, t), 2.95 (2H, t), 3.18 (4H, m), 3.45 (4H, m), 3.60 (20H, t), 3.72 (4H, m) 4,01 (2H, m) 16301104 170 Example 3 0.86 (12H, t), 1.14-1.52 (27H, m), 1.85 (2H, m), 2.06 (3H, s), 2.57 (2H, t), 2.85 (2H, t), 2.95 (2H, t) , 3.45 (4H, m), 3.61 (20H, t), 4,02 (2H, m) 16371100 172 Example 4 0.86 (12H, t), 1.15-1.51 (27H, m), 1.84 (2H, m), 2.07 (3H, s), 2.57 (2H, t), 2.85 (2H, t), 2.95 (2H, t) , 3.18 (4H, m), 3.45 (4H, m), 3.62 (20H, t), 3.72 (4H, m) 4,01 (2H, m) 16301100 171 Example 5 0.85 (12H, t), 1.13-1.50 (27H, m), 1.85 (2H, m), 1.96 (3H, s), 2.04 (3H, s), 2.07 (3H, s), 2.57 (2H, t) , 2.85 (2H, t), 2.95 (2H, t), 3.44 (4H, m), 3.60 (36H, t), 4,01 (2H, m) 16311102 171 Example 6 0.87 (12H, t), 1.14-1.49 (27H, m), 1.86 (2H, m), 1.96 (3H, s), 2.04 (3H, s), 2.07 (3H, s), 2.56 (2H, t) , 2.84 (2H, t), 2.95 (2H, t), 3.17 (4H, m), 3.44 (4H, m), 3.63 (36H, t), 3.71 (4H, m) 4,03 (2H, m) 16341103 170 Example 7 0.88 (12H, t), 1.12-1.48 (27H, m), 1.84 (2H, m), 1.97 (3H, s), 2.05 (3H, s), 2.09 (3H, s), 2.56 (2H, t) , 2.83 (2H, t), 2.94 (2H, t), 3.60 (172H, t), 3.45 (4H, m) 4,03 (2H, m) 16311103 170 Example 8 0.86 (12H, t), 1.13-1.49 (27H, m), 1.85 (2H, m), 1.96 (3H, s), 2.03 (3H, s), 2.07 (3H, s), 2.54 (2H, t) , 2.85 (2H, t), 2.94 (2H, t), 3.16 (4H, m), 3.45 (4H, m), 3.61 (172H, t), 3.74 (4H, m) 4,01 (2H, m) 16351101 171 Example 9 0.85 (12H, t), 1.12-1.48 (36H, m), 1.84 (2H, m), 1.97 (3H, s), 2.04 (3H, s), 2.09 (3H, s), 2.56 (2H, t) , 2.85 (2H, t), 2.95 (2H, t), 3.60 (4H, s), 3.45 (4H, m) 4,02 (2H, m), 5.11 (2H, m) 16341100 170 Example 10 0.85 (12H, t), 1.14-1.50 (45H, m), 1.85 (2H, m), 1.96 (3H, s), 2.04 (3H, s), 2.07 (3H, s), 2.57 (2H, t) , 2.85 (2H, t), 2.95 (2H, t), 3.44 (4H, m), 3.61 (10H, s), 4,02 (2H, m), 5.12 (2H, m) 16351102 171

Test Example 1 Comparison of Solubility of Concentration Transition Liquid Crystal Formation

After dissolving each of the natural ceramide (Ceramide type 3) and the samples of Examples 1 to 10 of the formula (3) in each solvent of Table 2 at 80 ℃, and then cooled to 20 ℃, the solubility for each solvent was measured The results are shown in Table 2 below.

Solvent Natural Ceramide Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 ethanol <1% 20% 20% 20% 20% 20% 20% 20% 20% 20% 20% Octyldodecanol <1% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% Octyl palmitate <1% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% Isopropyl Palmitate <1% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10% Cetyloctanoate <1% 10% 10% 10% 10% 10% 10% 10% 10% 10% 10%

(Formulation Examples 1-10 and Comparative Examples 1-2)

The components shown in Table 3 below were heated, dissolved and mixed with the aqueous and oil phases, followed by stirring and cooling to room temperature to prepare a cream.

ingredient Comparative example Formulation example One 2 One 2 3 4 5 6 7 8 9 10 Cetostearyl alcohol 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Lipophilic glycerin stearic acid 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Monostearic acid polyoxyethylene glycerine 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Self-emulsifying monoglycerate glycerin 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Tri (capryl, capric acid) glycerin 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 Liquid paraffin 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 Squalane 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Tocopheryl Acetate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Natural ceramide (ceramide type 3) - 1.0 - - - - - - - - - - Example 1 - - 1.0 - - - - - - - - - Example 2 - - - 1.0 - - - - - - - - Example 3 - - - - 1.0 - - - - - - - Example 4 - - - - - 1.0 - - - - - - Example 5 - - - - - - 1.0 - - - - - Example 6 - - - - - - - 1.0 - - - - Example 7 - - - - - - - - 1.0 - - - Example 8 - - - - - - - - - 1.0 - - Example 9 - - - - - - - - - - 1.0 - Example 10 - - - - - - - - - - - 1.0 Stearic acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 cholesterol 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Allantoin 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Glycine 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 glycerin 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 1,3-butylene glycol 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 7.0 Xanthan Gum 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Placenta Extract 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Hyaluronic Acid Extract 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Green Tea Extract 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 antiseptic q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. incense q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. Purified water To 100

Test Example 2 Liquid Crystal Formation Test

Using the polarizing microscope, the cream cosmetics prepared in Formulation Examples 1 to 10 and Comparative Examples 1 and 2 were observed using a polarization microscope to observe the distinctive cross-shaped appearance caused by the birefringence of the liquid crystal. It is shown in Table 4 below. In addition, the liquid crystal formation of the cosmetic product of Formulation Example 1 was observed with a polarizing microscope NIKON OPTIPHOT-2, and a photograph thereof is shown in FIG. 1.

Sample name Comparative example Formulation example One 2 One 2 3 4 5 6 7 8 9 10 Liquid crystal formation × ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

Test Example 3 Skin Safety Test

A routine patch test was conducted to test the safety of the skin. The 120 people were divided into 12 groups, the creams prepared in Formulation Examples 1 to 10 and Comparative Examples 1 and 2 were divided into groups to be used on the face for 10 days, and then scored according to the intensity of the stimulation as follows. The average value was calculated and the results are shown in Table 5 below.

(Score)

4: Very irritating, not suitable for use as a cosmetic.

3: It is good to not use because of severe irritation.

2: Slightly irritating and need attention when using.

1: Almost no irritation.

0: No irritation at all, good for sensitive skin.

Sample name Comparative example Formulation example One 2 One 2 3 4 5 6 7 8 9 10 Judgment 0.3 0.3 0.2 0.3 0.3 0.3 0.2 0.2 0.2 0.2 0.3 0.3

From the results of Table 4, there is no significant difference between each sample, but there is little irritation, it can be evaluated that the novel concentration-transition liquid crystal forming compound of the present invention is suitable for use as a raw material for cosmetics.

Test Example 4 Recovery of Damaged Skin

The recovery effect of damaged skin was divided into 12 groups of 60 hairless guinea pigs, and the creams prepared in Formulation Examples 1 to 10 and Comparative Examples 1 and 2 were measured by dividing each group. It was like

A pintone chamber was used to patch the flanks of test animals with acetone for 30 minutes to cause irritation, and then 200 μl of test substance was applied to the patch. Stimulation induction and recovery were assessed by measuring the water loss through the stratum corneum (Epidermal Water Loss, TEWL) using an evaporimeter. Instrument measurements were made at 30 minutes, 1 hour, 2 hours, 4 hours, 6 hours and 8 hours before the acetone patch and after patch removal, and the results are shown in Table 6 below. The measured value of normal skin before acetone treatment was 0, and the value immediately after acetone treatment was 100, and the skin gradually recovered to a normal state.

Measurement time Immediately after acetone treatment (Unit: AU) After application of sample (unit: AU) 30 minutes 1 hours 2 hours 4 hours 6 hours 8 hours Comparative example 12 100100 98118 95118 9291 8278 8058 7751 Formulation example 1 2 3 4 5 6 7 8 9 10 100 100 100 100 100 100 100 100 100 100 98104999999989810199100 951059795969594969795 61736165636565656462 51605252515254535552 40514045424544454342 32313533313334323333

As can be seen from the test results of Formulation Examples 1 to 10 of Table 6, the cream to which the novel concentration-transformation type liquid crystal formation was added showed a remarkable recovery ability of the damaged skin as compared to the cream without addition, and natural ceramide It showed similar recovery ability.

Test Example 5 Defense Test

The protective effect was measured by dividing 60 hairless guinea pigs into 12 groups and the creams prepared in Formulation Examples 1 to 10 and Comparative Examples 1 and 2 to each group, and the test method is as follows.

The test material was applied to the side of the test animal once a day for 7 days, and then patched with 2.5% SDS (sodium dodecyl sulfate) for 30 minutes using a pin chamber to determine the degree of irritation induced. Using an evaporation meter, the degree of stimulation induced immediately before the patch, 1 hour after the patch removal and 24 hours after the patch was measured, and the results are shown in Table 7 below.

Measurement time Just before the patch (Unit: AU) Patch Removal 1 hour later (Unit: AU) After 24 hours (unit: AU) Comparative example 12 1010 2523 1915 Formulation example 1 2 3 4 5 6 7 8 9 10 10101010101010101010 15161416161515161616 11121112131312121113

Test Example 7: Antioxidant Test

The antioxidant power of the compounds obtained in Examples 1 to 10 of the present invention was measured by the following two methods, and compared with the antioxidant power of vitamin E and vitamin E acetate to compare the antioxidant effect.

Test Example 7-1 Antioxidant Activity Test Using DPPH

Diphenylpicrylhydrazyl (DPPH) is a strong radical reaction inhibitor that reacts with radicals to form a stable compound. That is, about 50ml of DPPH was added to the test tube, the measurement material was added dropwise, and maintained at 37 ° C for about 30 minutes in a water bath. At this time, the sample without color change means that there is no antioxidant, and when it is difficult to measure with the naked eye, it is measured by UV, and the results are shown in Table 8 below.

Test Example 7-2: Antioxidant Test Using Linoleic Acid

In the experiment that the linoleic acid is easily oxidized to a compound having two double bonds and changed into a peroxide, a control sample solution containing 2.88 ml of 2.5% linoleic acid ethanol solution and 9 ml of 40mM phosphate buffer (pH 7.0) in 200 ml of ethanol The sample was taken at regular intervals while keeping the temperature in the dark at 40 ° C., and the time that the sample did not change was defined as the duration of antioxidant activity.

To 0.1 ml of the mixture prepared above, 9.7 ml of 75% ethanol and 0.1 ml of 30% ammonium thiocyanate were added, 0.1 ml of each sample was added dropwise, and after 3 minutes, UV absorbance was measured at 500 nm. The results are shown in Table 8 below. For reference, the lower the absorbance value, the better the antioxidant properties.

sample Test Example 7-1 Test Example 7-2 (UV (500 nm) absorbance) Control sample - 1.17 Example 1 Change to brown 0.23 Example 2 Change to brown 0.29 Example 3 Change to brown 0.30 Example 4 Change to brown 0.31 Example 5 Change to brown 0.34 Example 6 Change to brown 0.29 Example 7 Change to brown 0.26 Example 8 Change to brown 0.31 Example 9 Change to brown 0.30 Example 10 Change to brown 0.33 Vitamin E Change to brown 0.23 Vitamin E Acetate No color change 0.44

As can be seen from the results of Table 8, the liquid crystal forming material of the present invention shows an antioxidant power similar to that of vitamin E, and has a significant antioxidant power compared to the control sample.

As can be seen from the above, the concentration transition type liquid crystal forming compound of the general formula (I) provided by the present invention forms stable liquid crystals when applied to the skin to continuously supply moisture to the skin and at the same time by external environment. It can be used for the recovery and prevention of damaged skin, and it can release the tocopherol gradually to prevent the aging of the biological membrane. In addition, it can be used in the cosmetic composition is not limited in content when formulated in the cosmetic composition by increasing the solubility in the solvent.

Claims (9)

A novel concentration transition liquid crystal forming compound represented by the following general formula (I). [Formula 1] (I) In the above formula, n is an integer between 0 and 60, A is -CH _2- , -CHCH _3- , D ¹ and D ² are the same as or different from each other, and are hydrogen or an alkyl group containing C ₁ to C ₃₁ straight or branched chain, saturated or unsaturated, with or without a hydroxyl group, R is a substituent having the following structure. : Wherein B is a methyl group at the 5, 7 or 8 position of tocopherol, m is 1 to 3, D is -CH ₂ -CH (CH ₃ )-or -CH = C (CH ₃ )-.) The novel concentration transfer type liquid crystal forming compound according to claim 1, represented by the following general formula (I-1). (I-1) In the above formula, n, A and R are as defined in the general formula (I) above. The novel concentration transfer type liquid crystal forming compound according to claim 1, represented by the following general formula (I-2). (I-2) In the above formula, D ³ and D ⁴ are the same as or different from each other, and are a C ₁ to C ₃₁ straight or branched chain, saturated or unsaturated, an alkyl group containing or without a hydroxyl group, and n, A and R are represented by the general formula (I) As defined. (1) a step of preparing a diamide compound by mixing an O, O'-bis (2-aminopropyl) polyalkylene glycol with an alkali or organic base and tocopherylsuccinic chloride and then reacting: and (2) dissolving the diamide compound prepared in step (1) in an organic solvent, followed by filtration to remove insoluble materials and recrystallize and purify: Method for producing a concentration-transition liquid crystal-forming compound of formula (I-1) of claim 2 comprising a. (1) O, O'-bis (2-aminopropyl) polyalkylene glycol is dissolved in dichloromethane or ethanol, and then reacted with a C ₁ to C ₃₁ halo alkyl group or an epoxy compound in an inert air stream to give a general formula (II) Steps to get intermediates: [Formula 2] (II) (Wherein D ³ and D ⁴ are the same as or different from each other, and C ₁ to C ₃₁ are linear or branched, saturated or unsaturated, alkyl groups containing or not containing hydroxyl groups, n and A are general formulas (I As defined in)): (2) mixing an alkali or organic base with the intermediate of Formula (II) and tocopheryl succinic acid obtained in step (1) and reacting to prepare a diamide compound; and (3) dissolving the diamide compound prepared in step (2) in an organic solvent, followed by filtration to remove insoluble materials and recrystallization to purify: Method for producing a concentration-transition liquid crystal-forming compound of formula (I-2) of claim 3 comprising a. The polyalkylene glycol unit in the O, O'-bis (2- (2-aminoethyl) propyl) polyalkylene glycol is one selected from the group consisting of 1 to 60. And alkylene is ethylene or propylene, and the halo epoxy compound is epichlorohydrin, epibromohydrin, 3,4-epoxy-1-chlorobutane, 3,4-epoxy-1-bromobutane, 4,5 -Epoxy-1-chloropentane, 4,5-epoxy-1-bromopentane, a method for producing a concentration-transition liquid crystal forming compound, characterized in that one selected from the group consisting of. The method of claim 4 or 5, wherein the alkali is one selected from the group consisting of potassium hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, magnesium oxide, potassium oxide, the organic base is triethylamine, diisopropylethylamine or Method for producing a concentration-transition liquid crystal-forming compound characterized in that it is pyridine. The method of claim 4 or 5, wherein the organic solvent is one selected from the group consisting of an alcohol solvent, a halogen solvent, a hydrocarbon solvent, and an ester solvent. A cosmetic composition comprising the concentration transition liquid crystal forming compound of formula (I) according to claim 1 in an amount of 0.001 to 30% by weight based on the total weight of the composition.