KR20200092188A - Composition for hair dye comprising polymer of cationic polymer and gardenia yellow pigment with increased hair permeability as effective component - Google Patents

Abstract

The present invention relates to a composition for a hair dye containing a cationic polymer with increased hair permeability and a gardenia yellow polymer as an active ingredient. The cationic polymer and gardenia yellow polymer of the present invention can be developed as a hair dye that does not have side effects on a human body using natural pigments, have excellent dyeing properties and dyeing persistence of hair, and alleviate damage to the hair, thereby being usefully used in hair dye-related industries.

Description

Composition for hair dye comprising polymer of cationic polymer and gardenia yellow pigment with increased hair permeability as effective component}

The present invention relates to a composition for a hair dye containing a cationic polymer having increased hair permeability and a polymer of gardenia yellow as an active ingredient.

Human hair is different in color and shape depending on race, and it is common to dye in various colors for beauty purposes. Hair dyeing is advancing in the direction of pursuing various colors from black-brown one-sidedness in accordance with the trend of the age that values individuality.

In the case of conventional hair dyeing, temporary dyeing based on tar color and semi-permanent dyeing based on oxidizing dye are used, and both methods use chemical synthetic hair dye as the main component. These synthetic hair dyes contain potential harmful factors that cause cancer, including leukemia, bladder cancer, uterine cancer and breast cancer, when used frequently with hair damage, rash and contact skin reactions, and visual impairment. Therefore, it is required to develop a natural hair dye that is harmless to the human body and is environmentally friendly, and henna is a representative material as a natural hair dye. In addition, ink, walnut, indigo, and chamomile are used. Henna is red, walnut is brown, ink is black, indigo is blue, and chamomile is yellow. Shows. Vegetable natural dyes are highly applicable to hair dyes because they contain hydrophilic and hydrophobic groups that are abundant to adsorb on hair.

As a limitation of the use of natural pigments in hair dyeing, it has a low solubility in organic solvents compared to synthetic dyes, and has problems in reproducibility, standardization, instability in raw material supply, and expensive raw material costs. Was not actively done. In the present invention, by using a by-product of a plant resource that is cheap in raw material cost and easy to supply raw materials, it identifies natural pigments with excellent color development power and combines them with cationic polymers to secure structural stability and increase the adsorption effect on damaged hair with negative ions. It is intended to be applied to hair dye.

Gardenia jasminoides is an evergreen broad-leaved shrub of the family Rubiaceae, and when the oval fruit matures from September to November and shows a reddish yellow color, it is collected and dried to be used for medicinal and dyeing purposes. In particular, in oriental medicine, it is used to treat diuretics, antipyretics, sedatives and eye diseases, jaundice, and is important as a hemostatic agent.

On the other hand, Korean Patent Publication No. 2013-0143296 discloses a'hair dye composition containing gardenia yellow pigment and citrus leaf oil', and Korean Registered Patent No. 1662731 describes a method of manufacturing acylated natural dyes. Acylated natural dyes and hair dyes comprising the same are disclosed. However, the composition for hair dyes containing the cationic polymer having increased hair permeability and a polymer of gardenia yellow as an active ingredient has not been disclosed.

The present invention was derived by the above-mentioned needs, and the present inventors mixed 30 to 35 parts by weight of gardenia yellow with respect to 100 parts by volume of an aqueous solution of cationic polymer polyethyleneimine, and then added water to the mixture. When the polymer synthesized by reacting at 55 to 65°C for 5 to 10 hours was treated to hair, the color was high, the wash fastness was excellent, the damage to the hair was reduced, and the hair permeability was significantly increased, confirming that the present invention Was completed.

In order to solve the above problems, the present invention provides a composition for hair dyes containing a cationic polymer and a polymer of gardenia yellow as an active ingredient.

The cationic polymer of the present invention and the polymer of gardenia yellow pigment can be developed as a hair dye without side effects to the human body using natural pigments, and it is excellent in dye-related industries because it is excellent in dyeing and dyeing durability of hair and alleviates hair damage. It can be useful.

1 is a result of HPLC analysis of crosin (A) and crocetin (B) standards and gardenia yellow (C).
Figure 2 is a result of confirming whether the polymerization of the polymer prepared by the synthesis time by TLC to compare the synthesis amount of the cationic polymer and the polymer of the pigment (PGYP) according to the synthesis time. GY represents a gardenia yellow pigment primary color.
Figure 3 is a result of confirming the cytotoxicity of the cationic polymer of the present invention and a polymer of gardenia yellow (PGYP). GY represents the primary pigment of gardenia yellow, and PEI represents the polyethyleneimine, a cationic polymer.
4 is a cationic polymer of the present invention and a polymer (PGYP) of gardenia yellow pigment and gardenia yellow pigment (GY), respectively, dyed in hair for 40 minutes at room temperature, and then the color number using a color difference meter (color index) It is the result of measuring. GY represents a gardenia yellow pigment primary color.
Figure 5 is a cationic polymer of the present invention and the polymer of the pigment (PGYP) and gardenia yellow pigment (GY) of dyeing the hair for 40 minutes at 40 ℃ each, and then using a color difference color index (color index) ). GY represents a gardenia yellow pigment primary color.
Figure 6 is a cationic polymer of the present invention and the polymer of the gardenia yellow pigment (PGYP) and the gardenia yellow pigment primary pigment (GY), respectively, dyed in the hair for 40 minutes at room temperature, the dyed hair using neutral shampoo 10 times It is the result of measuring the color index after washing until. GY represents a gardenia yellow pigment primary color.
Figure 7 is a cationic polymer of the present invention and the polymer of the gardenia yellow pigment (PGYP) and the gardenia yellow pigment primary pigment (GY) after dyeing the hair for 40 minutes at 40 ℃, 10 times using a neutral shampoo dyed hair It is the result of measuring the color index after washing up to ash. GY represents a gardenia yellow pigment primary color.
8 is a result of confirming the appearance characteristics of the cationic polymer of the present invention and a polymer (PGYP) of gardenia yellow and gardenia yellow (GY), respectively, dyed with a scanning electron microscope (SEM). . A is virgin hair; B is bleaching hair; C is hair treated with a gardenia yellow pigment (GY); D denotes hair treated with a cationic polymer and a gardenia yellow polymer (PGYP).
FIG. 9 shows hair permeability of PGYP and GY through FITC fluorescence expression after dyeing the hair with a cationic polymer labeled with FITC (Fluorescein isothiocyanate) and a polymer of gardenia yellow (PGYP) and a gardenia yellow pigment (GY), respectively. Is the result of checking. A indicates that fluorescence expression is confirmed in the cuticle when hair is dyed with GY, and B indicates that fluorescence expression is confirmed not only in the epidermis but also in the cortex when dyeing hair with PGYP. , C and D, respectively, confirmed the FITC fluorescence expression of the cross-section of hair dyed with PGYP and GY, indicating that the hair permeability is better when dyed with PGYP(D) than GY(C).

In order to achieve the object of the present invention, the present invention provides a composition for hair dyes containing a cationic polymer and a polymer of gardenia yellow as an active ingredient.

In the composition for hair dyes according to an embodiment of the present invention, the cationic polymer may be polyethyleneimine, preferably linear polyethyleneimine or branched polyethyleneimine, It is not limited to this.

In addition, in the composition for a hair dye according to an embodiment of the present invention, the gardenia yellow may be crocin, but is not limited thereto.

In addition, the gardenia yellow is

1) obtaining an aqueous solution of yellow pigment from gardenia fruit; And

2) removing the precipitate by adding ethanol to the aqueous solution of yellow pigment obtained in step 1), adding ethanol and ethyl ether, and then leaving at 3 to 5° C. to obtain gardenia yellow; It may be, but is not limited to this.

In addition, the cationic polymer and the polymer of gardenia yellow are

1) adding and mixing 30 to 35 parts by weight of gardenia yellow with respect to 100 parts by volume of a cationic polymer aqueous solution; And

2) adding water to the mixture of the cationic polymer and gardenia yellow of step 1) to react for 5-10 hours at 55-65° C.; preferably, it may be prepared including 1) cation Adding and mixing 35 parts by weight of gardenia yellow with respect to 100 parts by volume of the aqueous polymer solution; And

2) adding water to the mixture of the cationic polymer and gardenia yellow of step 1) to react at 60° C. for 5 hours; but may be prepared including, but not limited to.

In addition, the aqueous solution of the cationic polymer in step 1) may include 20 to 40 parts by weight of a cationic polymer with respect to 100 parts by volume of water, preferably 30 parts by weight of a cationic polymer. It is not limited.

In addition, the cationic polymer and the polymer of gardenia yellow pigment may be included in 0.0001 to 20 parts by weight based on 100 parts by weight of the hair dye composition, but is not limited thereto.

When the cationic polymer and the polymer of gardenia yellow are less than 0.0001 parts by weight with respect to 100 parts by weight of the hair dye composition, the pigmentation is weak and the coloring effect of the hair is little, and when it exceeds 20 parts by weight, the coloring of the entire formulation becomes excessive. It is undesirable because it becomes too bright.

In the hair dye composition of the present invention, a pH adjusting agent is used to improve dyeability, and examples thereof include L-arginine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and potassium hydroxide ( alkali agents such as potassium hydroxide, sodium hydroxide, sodium carbonate, aminomethyl propanol, ammonia water, phosphoric acid, lactic acid, glycolic acid, citric acid ), organic acids such as acetic acid, hydrochloric acid, and sulfuric acid, and inorganic salts, and salts thereof, and the like, and is not particularly limited in its kind, and a pH adjusting agent usually used for hair dyes can be used.

In the hair dye composition of the present invention, a reducing agent is used for improving hair dyeability and stabilizing iron salts, for example, sulfites such as sodium pyrosulfite and sodium sulfite, and salts thereof, disodium pyrophosphate, trisodium Pyrophosphates or phosphates such as trisodium pyrophosphate, tetrasodium pyrophosphate, vitamin derivatives such as propylgallate, ascorbic acid, erythorbic acid, and cysteine And cysteine derivatives such as hydrochloride, sodium thiosulfate, sodium hexahydroxostannate, thioglycolic acid and thiolactic acid, and the like. A reducing agent can be used.

When the hair dye composition of the present invention is applied to hair, a thickener that serves to improve the convenience of use while preventing problems such as dripping, is a starch, a water-soluble polymer, hydroxyethylcellulose, polyquaternium and cellulose. Cellulose gum and the like.

In addition, the composition for the hair dye is hair tint, eyebrow, tattoo formulation, hair nutrition lotion, hair treatment, hair shampoo, hair rinse, hair cream, hair wax, hair aerosol, hair pack, hair soap, hair dye, hair wave First, it may be prepared as one formulation selected from the group consisting of hair essences and hair conditioners, but is not limited thereto.

Hereinafter, it will be described in detail by examples of the present invention. However, the following examples are only to illustrate the present invention, the content of the present invention is not limited to the following examples.

Example One. Gardenia yellow Active ingredient content analysis

Gardenia yellow (GY) used in the present invention was obtained by adding ethanol to an aqueous yellow pigment obtained from gardenia fruit to remove precipitates, and adding ethanol and ethyl ether to stand at 4°C. When extracting yellow pigment from gardenia fruits, there may be cases in which crocetin is included, but in the presence of crocetin, the quality of the pigment is deteriorated. Thus extracted Analysis was performed using high-performance liquid chromatography (HPLC) to check the content of crosine and presence of crocetin in gardenia yellow (hereinafter referred to as'sample') (Table 1). Gardenia yellow was prepared at 1mg/ml, diluted 10-fold, filtered with a syringe filter (0.45㎛, syinge-driven filter unit, ADVENTEC, Ehime, Japan) and used for HPLC analysis. Crosin and crocetin standards (Sigma-Aldrich Co., St. Louis, MO, USA) was used to prepare at 1 mg/ml, and crosine was diluted to concentrations of 1, 2, 4, 6, 8 and 10 μg/ml and used. Settin was used at a concentration of 1, 10, 20, 30, 40 and 50 µg/ml.

As a result, the crosin standard was able to confirm the peak (R ² =0.9965945) at RT (retention time) 9.769, and for the crocetin standard, the peak (R ² =0.9998863) was confirmed at RT 27.332 (FIG. 1A and 1B). As a result of substituting the sample of 0.1 mg/ml of gardenia yellow for 3 times and substituting it into the calibration curve, the content of crosine was measured to be 2.7123 µg/ml, 2.3452 µg/ml and 2.2034 µg/ml, respectively, and averaged 2.4203 ± 0.2144 µg. It was confirmed that /ml (Table 2), and when calculated as the content per gram of the sample, it was confirmed that the extracted gardenia yellow contained 24.203 mg/g of crosine. In the case of crocetin, a peak having the same RT could not be detected (FIG. 1C ), and it was confirmed that crocetin was not present in gardenia yellow (Table 2). Therefore, in the subsequent analysis, the index component of gardenia yellow was designated as crosin, and the following example was performed.

HPLC analysis conditions equipment Shimadzu LC-20A column YMC Pack ODS-AM Oven temperature 30℃ Detector UV-VIS detector wavelength 443 nm Solvent A water Solvent B Acetonitrile flux 1ml/min Injection volume 20 μl Mobile phase gradient Dissolution time (min) Solvent A (%) Solvent B (%) 0 80 20 0-20 20 80 20-25 20 80 25-35 80 20 35 45 80 20

Crosin and crocetin content measurement results compound Gardenia yellow (µg/ml) Crosin Crocetin Sample number One 2.7123 - 2 2.3452 - 3 2.2034 - Average 2.4203 ± 0.2144 -

-; Not detected

Example 2. Cationic Polymer and Gardenia yellow polymer( PGYP ) Establish synthesis conditions

1) according to the temperature Gardenia yellow Stability evaluation

When synthesizing a cationic polymer and a polymer of gardenia yellow (PGYP), in order to establish a synthesis temperature, stability evaluation of gardenia yellow according to temperature was performed. A proton yellow pigment (GY) of 1 mg/ml was prepared and analyzed after bathing at room temperature, 45° C., 60° C., 75° C. and 90° C. for 5 hours, respectively. As a result, the content of crosine was 37.78275 μg/ml at room temperature, 30.03999 μg/ml at 45° C., 18.37164 μg/ml at 60° C., 10.37444 μg/ml at 75° C., and 3.32795 μg/ml at 90° C., and content per g The results were calculated as 37.78275 mg/g, 30.03999 mg/g, 18.37164 mg/g, 10.37444 mg/g and 3.32795 mg/g, respectively, when the content at room temperature was 100%, 79.51% at 45°C, 60°C From 48.62%, 27.46% at 75°C and 8.81% at 90°C, it was confirmed that the content of crosine decreased as the temperature increased (Table 3).

Measurement of crosine content according to temperature treatment in gardenia yellow Temperature Crosin (µg/ml) % (Compared to room temperature) Room temperature 37.78275 100.00 45℃ 30.03999 79.51 60℃ 18.37164 48.62 75℃ 10.37444 27.46 90℃ 3.32795 8.81

2) Cationic Polymer and Gardenia yellow Confirmation of polymerization

To synthesize polymerized natural pigment, 0.1 g of polyethyleneimine (Mn = 7,000, branched, PDI = 1.2, Sigma-Aldrich Co., St. Louis, MO, USA) 0.2 g of gardenia yellow pigment (GY ), dissolved in 2 ml of distilled water and reacted hourly (1, 3, 5, 10 and 15 hours) by connecting a reflux cooler at 90°C to prepare a cationic polymer and a polymer of gardenia yellow (PGYP) Did. After the reaction, the mixture was diluted with 100 ml of distilled water, washed with dichloromethane (DCM) three times, and then concentrated to prepare a sample. By preparing a cationic polymer and a polymer of gardenia yellow by time (PGYP), and confirming this by TLC, as shown in FIG. 2, a dark brown fluorescent spot could be observed at a R _f value of 0.63 in the crosine standard. It was also possible to confirm the yellow pigment. In addition, the spots could be identified at the same location in the primary pigment (GY) of the gardenia yellow pigment, and the spots could be identified at the same location from 1 hour to 3 hours in PGYP, but were not observed from 5 hours. Therefore, the optimal time for the reaction was confirmed that the reaction of 90 °C, polyethyleneimine (PEI) and gardenia yellow were completely polymerized in a reaction of 5 hours or more. In addition, it was confirmed that a new spot that does not exist and does not separate is formed under UV illumination at 356 nm (FIG. 2). This spot is a cationic polymer and a polymer of gardenia yellow (PGYP), and it is judged that it cannot be separated by TLC due to its high molecular weight.

3) Cationic Polymer and Gardenia yellow Establishment of polymer synthesis time

In the same manner, a cationic polymer and a gardenia pigment polymer (PGYP) were prepared by time, and each hourly sample was analyzed for crosin using HPLC, and in the PGYP sample prepared by reacting by time, crosin (RT value) =9.54min) was not observed, and as time passed, new peaks with RT values of 19 and 22 were induced. As the reaction time elapsed, the content increased to show the maximum content at 10 hours and thereafter did not show a large content change (Table 4). This means that a new compound is formed by polymerization of crosine and polyethyleneimine with each other, and it can be said that the optimum reaction time is 10 hours or less.

Retention time (RT) and area according to the polymer synthesis time Composite time (hour) RT Area One 18.956 35230.0 22.056 2951.3 3 18.697 50396.2 21.930 3016.0 5 19.417 541896.9 22.203 62770.2 10 19.206 818978.1 22.065 67876.5 15 20.183 33270.8 20.250 231465.0 21.925 77506.6

4) Cationic Polymer and Gardenia yellow Establishing the synthesis temperature of the polymer

For comparison of the synthetic amount of cationic polymer and gardenia yellow polymer (PGYP) according to temperature, 0.102 g of polyethyleneimine (PEI, Mn=7,000, PDI=1.2, Sigma-Aldrich Co., St. Louis, MO, USA ), after adding 0.2 g of gardenia yellow (GY), dissolve it in 2 ml of distilled water and connect a reflux cooler heated by temperature (45℃, 60℃, 75℃ and 90℃) for 5 hours. The reaction was performed to prepare PGYP. After the reaction, the mixture was diluted with 100 ml of distilled water, washed three times with dichloromethane (DCM), and then concentrated to be used as an HPLC analysis sample. As a result, no peak was found at 45°C, and the peak values were confirmed in the 21st and 23rd minute RT values in the sample (PGYP) prepared by reacting at 60°C, 75°C, and 90°C. It is considered to be a sex polymer and a polymer of gardenia yellow (PGYP). In addition, synthesis was started from 60°C, and as the temperature increased, it was confirmed that the amount of polymer synthesis increased. When synthesized with the results of stability evaluation of gardenia yellow according to the synthesis temperature, synthesis started and the amount of pigment was about 50% (compared to room temperature). The following examples were carried out by establishing the remaining 60°C as the optimum condition.

Retention time (RT) and area according to the polymer synthesis temperature Synthesis temperature (℃) RT Area 45 - - 60 21.102 384266.4 23.577 105632.3 75 21.071 359208.4 23.369 213529.0 26.531 147378.8 90 21.000 388144.8 23.236 109375.7

-; Not detected

5) Cationic Polymer and Gardenia yellow Titration of polymer Gardenia yellow amount Establish

Since it is not possible to directly confirm whether the synthesis of the cationic polymer and the polymer of the gardenia yellow pigment (PGYP) is completed, it is to establish an appropriate pigment amount by analyzing the remaining gardenia yellow pigment that has not been synthesized. Therefore, for the synthesis of PGYP, 20, 25, 30, 35, 40, 45, 50 and 100 ml of polyethylenimine aqueous solution containing 30 parts by weight of polyethyleneimine (PEI, Mn=7,000) with respect to 100 parts by weight of water and 55 g of gardenia yellow (GY) was added and dissolved to connect a reflux cooler heated to 60° C. and reacted for 5 hours to be used as an HPLC analysis sample.

As a result, as shown in Table 6 below, peaks of crosine could not be confirmed in PGYP of 20g/100ml, 25g/100ml and 30g/100ml, but 2.70689µg/ml of croissant in 35g/100ml PGYP Confirmed God. Since 40g/100ml, gradually increasing crosin content, and through these results, when reacting by adding 31~35g of gardenia yellow to 100ml of polyethyleneimine, polyethyleneimine (PEI), a cationic polymer It is judged that the synthesis ratio of perilla yellow pigment (GY) is appropriate.

Crosin content of polymer according to the amount of gardenia yellow added Pigment content (g/ml) Crosin (µg/ml) GY PGYP 20 115.4474 - 25 154.8337 - 30 209.9894 - 35 393.5756 2.70689 40 452.2102 20.92404 45 469.7420 21.84520 50 570.5491 103.53300 55 663.5618 104.84870

-; Not detected

Example 3. Cationic Polymer and Gardenia yellow Polymer Antioxidant Efficacy Assay

The antioxidant efficacy assay of the cationic polymer and the polymer of gardenia pigment (PGYP) was confirmed by ABTS radical scavenging activity assay. Specifically, ABTS[2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid)-diammonium salt] reagent is added to 2.4mM potassium persulfate in 7.4mM ABTS and 12 in a dark room at 25°C. It was used after reacting for a period of time. Gardenia yellow pigment (GY), cationic polymer and gardenia yellow polymer (PGYP) and polyethyleneimine (PEI) were respectively 17.5, 35, 46.7, 70, 140 and 350 µg/ml. After preparing to a concentration of 800 μl, ABTS reagent was added to 400 μl and reacted in the dark for 10 minutes, and absorbance was measured using a UV-1650PC UV/VIS spectrophotometer (Shimadzu, Kyoto, Japan) at 734 nm. As standard, L(+)-ascorbic acid (Junsei Chemical Co., Ltd, Tokyo, Japan) was prepared and used at 2, 4, 6, 8 and 10 µg/ml, and RC ₅₀ , which is a concentration that inhibits radicals by 50%. Values were compared. As a result, as shown in Table 7 below, in the case of polyethyleneimine (PEI), which is a cationic polymer, the concentration of inhibiting radicals by 50% is 187.089 µg/ml, and 310.984 µg in the case of gardenia yellow pigment primary pigment (GY). /Ml, whereas the cationic polymer of the present invention and the polymer of gardenia yellow (PGYP) was 93.313 µg/mL, confirming that it exhibits higher antioxidant activity than treatment with polyethyleneimine (PEI) and gardenia yellow (GY) alone. Did.

Antioxidant activity of cationic polymer and polymer of gardenia yellow sample RC ₅₀ (µg/ml) L(+)-ascorbic acid 8.261 PEI 187.089 GY 310.984 PGYP 93.313

.

Example 4. Cationic Polymer and Gardenia yellow Evaluation of polymer cytotoxicity

The cells were used for pre-sale of human-derived keratinocytes, HaCaT cells, from the Korean Cell Line Bank (Seoul, Korea), and when HaCaT cells were contaminated by 70 to 80% every 2-3 days, 1: Passed 3 and used in the experiment. For the reagent, Dulbecco's modified Eagels's medium (DMEM), fetal bovine serum (FBS), 0.25 mM trypsin-EDTA, and penicillin/streptomycin (P/S) were used by Gibco (NY, USA) and PBS (pH7.4) ) Was used by AMRESCO (Solon, OH, USA). DMSO (dimethyl sulfoxide) used Cyroserv product of Mylan NV (canonsburg, PA, USA), and Sigma-Aldrich for MTT [3-(4,5-dimethyltiazol-2-yl)-2,5-diphenyltetrazolium bromide] The product of St. Louis, MO, USA was used. The culture of HaCaT cells was performed using DMEM medium to which 10% FBS and 1% penicillin/streptomycin were added, and cultured at 37°C and 5% CO ₂ .

Toxicity evaluation of HaCaT cells was confirmed by MTT analysis. After inoculating the cells in a 96-well cell plate with 1×10 ⁵ cells per well and incubating for 24 hours at 37° C. and 5% CO ₂ conditions, cationic polymer and gardenia yellow polymer (PGYP) and gardenia are used with PBS. The yellow pigment primary pigment (GY) and cationic polymer (PEI) were treated by diluting them at concentrations of 17.5, 35, 46.7, 70, 140 and 350 µg/ml, respectively. After 24 hours of sample treatment, the MTT solution (5 mg/ml in PBS) was treated to be 10 μl per 100 μl, and after reacting at 37° C. for 4 hours, the medium was removed to formazan with 200 μl DMSO (formazan). The crystal was dissolved. Absorbance was measured at a wavelength of 540 nm using an ELISA reader (VITOR X 2030 multilabel reader, PerkinElmer, Waltham, MA, USA), and the measured absorbance was expressed as a percentage (%) of the control value.

As a result, as shown in FIG. 3, the cationic polymer polyethyleneimine (PEI) showed a cell viability of 56.06% at the highest concentration of 350 μg/ml, which was the highest concentration, whereas it was confirmed that it was cytotoxic. Bovine primary pigments (GY) and cationic polymers and polymers of gardenia yellow pigments (PGYP) showed cell viability of 80% or higher at all treatment concentrations.

Example 5. Cationic Polymer and Gardenia yellow Hair dyeing and cleaning of polymer Color fastness Confirm

Hair samples were collected from Asian women in their 20s who did not undergo chemical treatment such as dyeing and bleaching, cut into approximately 10 cm lengths, collected, and treated with silicone for the upper part. The bleaching agent was bleach powder (bleach powder) and A'Wella Blonde' product composed of 2 agents, 6% peroxide, was used. For bleaching, after mixing 50 g of bleach powder and 100 g of 6% peroxide in a weight ratio of about 20 g, apply to the hair using a dyeing brush and leave it at 55° C. for 20 minutes, then lukewarm water. It was washed and dried with, and decolorization was performed twice in total. Hair dyeing was treated with 10 ml of proton yellow pigment primary pigment (GY) and cationic polymer and gardenia yellow pigment (PGYP) prepared at 35 g/100 ml for hair cut to 10 x 10 cm, respectively at room temperature and 40°C. After leaving it for 40 minutes, it was washed with running lukewarm water and analyzed for color difference.

In addition, in order to evaluate the fastness of cleaning of the hair, GY and PGYP were dyed at room temperature and 40°C, respectively, and D65-10 using a colorimeter (X-rite vs450, X-Rite Inc., Grand Rapids, MI, USA). It was measured in a light source and displayed in the CIELCh color space to compare and analyze L* (brightness), a* (red and green), and b* (yellow and blue) values. Each hair sample was thoroughly washed with lukewarm water using a neutral shampoo and then dried to measure the color difference based on the measured value immediately after dyeing. Up to 10 times were performed, and in order to exclude color difference according to height when measuring color difference, both ends of the hair were fixed and measured at the same height.

As a result, when analyzing the color difference of the hair dyed for 40 minutes at room temperature, the brightness value of the hair treated with the cationic polymer and the polymer of the gardenia pigment (PGYP) was lower than that of the gardenia yellow pigment (GY). The redness (a*) and yellowness (b*) values confirmed that PGYP showed higher red and yellow compared to GY (FIG. 4). In addition, as a result of the color difference analysis of the hair dyed for 40 minutes at 40° C., the PGYP brightness value was lower than GY, and the redness was PGYP and the yellowness was higher in GY than in the normal temperature result (FIG. 5).

As a result of analyzing the color fastness of the hair, it can be confirmed that PGYP is more dyeable than GY through color difference rendering (FIGS. 6 and 7), and these results show that the PGYP of the present invention exhibits high yellowness and redness. It means that it should be used as a non-heating dye.

Example 6. Cationic Polymer and Gardenia yellow Polymer appearance characteristics and hair permeability Confirm

One) Cationic Polymer and Gardenia yellow Appearance characteristics of polymer dyed hair

In order to confirm the appearance characteristics of the hair dyed with a cationic polymer and a polymer of gardenia pigment (PGYP), virgin hair, bleaching hair and gardenia pigment primary pigment (GY), cationic polymer and The surface of the hair sample was photographed by using a scanning electron microscope (SEM) on the hair stained with a polymer of gardenia yellow pigment (PGYP). After collecting the middle part of the dyed hair, the length of each hair sample was cut to 4 mm, and then attached by carbon tape on the treated aluminum stub. Then, platinum plating was performed for 240 seconds using an ion coating machine (PT plasma coater) and then observed at 15 kV with FE-SEM (scanning electron microscope, JSM-6701F, JEOL, Japan).

As a result of comparing the SEM images obtained through each hair, as shown in FIG. 8, the degree of damage of the cuticle layer, morphological change, and large differences in the surface of the hair were shown. In the case of bleaching hair, fur It was difficult to observe the normal cuticle layer necessary for vaginal protection, and the damage to the cuticle layer revealed all of the fibrous tissue in the cortex, such as bark, and part of the surface of the hair fiber was separated from the fiber and floated, separating the cuticle by discoloration. It was confirmed that disappearance and movement of scales and peeling occurred (FIG. 8B ). On the other hand, in the case of hair dyed with gardenia yellow pigment (GY) and cationic polymer and gardenia yellow polymer (PGYP), the pigment component is adsorbed to the cortex instead of the removed epidermal layer exposed by decolorization, and the cortex is exposed. However, in the case of gardenia yellow pigment primary pigment (GY), the exposed or exfoliated fur was not completely covered, and part of it was exposed or fluffed, and the movement and separation of the separated cutie layer was still observed. (Figure 8C). On the other hand, in the case of hair dyed with the cationic polymer of the present invention and the polymer of gardenia yellow (PGYP), the polymer was uniformly adsorbed on the cortex, and it was not possible to identify floating or separated cortical fibers, and the cutout layer that had been eliminated. No tissue was observed, and similar to the original hair (FIG. 8A), it was found that the entire epidermal layer was in the form of clear and healthy hair (FIG. 8D).

2) FITC ( Fluorescein isothiocyanate ) Labeled cationic polymer and gardenia yellow polymer permeability of hair

Pigmented by the pigmented fluorescein isothiocyanate (FITC) primary pigment (GY) and cationic polymers and polymers of gardenia pigment (PGYP) on the hair, respectively, and then pigmented by polyethylenimine (PEI) polymerization through FITC fluorescence expression. It was confirmed whether the increase in hair permeability. Specifically, FIG (Sigma-Aldrich Co., St. Louis, MO, USA), a fluorescent dye, was labeled for PGYP. 1 ml each of GY and PGYP was used, and in the case of PGYP, 0.01% of PEI (25 kDa, branched, Aldrich Chemicals, Milwaukee, WI, USA) was additionally added for cross-linking with FITC. Each sample was mixed in a carbonate buffer (0.5M, pH 9.0) containing 10 mg/ml of FITC and reacted for 2 hours at room temperature to be labeled, and unbound FITC was added to a Sephadex G25 column (Pharmacia, Uppsala, Sweden). Was removed. FITC-labeled GY and PGYP were stored at 4° C. until hair dyeing.

In order to visually confirm the transmission efficiency of a dye in hair dyeing using GY and PGYP, a fluorescence image restoration microscopy was used, and each stained sample was OCT embedding matrix (Cell Path Ltd. in a cryo mold). , UK) to freeze the tissue at 70°C. To confirm the degree of skin penetration of the fluorescent reagent to the dyed hair tissue, the hair tissue was observed with an Olympus IX70 Inverted Microscope, the excitation wavelength for FITC was 430/10 nm, and the emission wavelength was adjusted to 470/30 nm. In addition, in order to observe the longitudinal section of the dyed hair tissue, the frozen dyed hair tissue was cross sectioned to a thickness of 10 μm at 20° C. using a cryotome (HM505E, Germany) to prepare a section slide. Polyvinyl alchol mounting medium with DABCO (Sigma-Aldrich Co., St. Louis, MO, USA) was treated to reduce photobleaching and increase the adhesion between hair tissue and cover glass. It was observed.

As a result, as shown in FIG. 9, when FITC-labeled gardenia yellow pigment (GY) was dyed on the hair, FITC fluorescence expression was transmitted to the cuticle composed of about 10-15 layers of keratin layers. It was stained, especially when dyeing hair with a cationic polymer and a gardenia pigment (PGYP), it was confirmed that FITC fluorescence was expressed not only in the epidermis but also in the cortex composed of fibrous cells (FIGS. 9A and 9B). .

In addition, even when GY and PGYP stained hair were cross sectioned and the fluorescence expression of FITC of the cut section was confirmed, it was confirmed that the hair permeability was better than GY in the entire section of hair stained with PGYP (FIG. 9C and Fig. 9D).

Claims (8)

A composition for hair dyes containing a cationic polymer and a polymer of gardenia yellow as an active ingredient. The composition for a hair dye according to claim 1, wherein the cationic polymer is polyethyleneimine. 3. The composition for a hair dye according to claim 2, wherein the polyethyleneimine is linear polyethyleneimine or branched polyethyleneimine. The composition for hair dye according to claim 1, wherein the gardenia yellow is crocin. According to claim 1, wherein the cationic polymer and the polymer of the gardenia yellow pigment
1) adding and mixing 30 to 35 parts by weight of gardenia yellow with respect to 100 parts by volume of an aqueous cationic polymer solution; And
2) adding the water to the mixture of the cationic polymer aqueous solution of step 1) and gardenia yellow for 5 to 10 hours at 55 to 65° C.; [6] The composition for hair dye according to claim 5, wherein the aqueous cationic polymer in step 1) contains 20 to 40 parts by weight of cationic polymer with respect to 100 parts by volume of water. According to claim 1, wherein the cationic polymer and the polymer of the gardenia yellow pigment is 0.0001 to 20 parts by weight based on 100 parts by weight of the composition for hair dye composition. According to claim 1, The hair tint for hair dye, eyebrow, tattoo formulation, hair nutrition lotion, hair treatment, hair shampoo, hair rinse, hair cream, hair wax, hair aerosol, hair pack, hair soap, hair dye, A composition for hair dyes, characterized in that it is prepared in one formulation selected from the group consisting of a wave agent for hair, a hair essence, and a hair conditioner.

Images