CATIONIC CELLULOSE AND COMPOSITION FOR TREATING HAIR, SKIN, OR FIBER INCLUDING SAME

Abstract

The present invention provides a composition for treating hair, skin, or fiber, comprising a cationic cellulose polymer. In the present invention, the cationic cellulose polymer may be used for various purposes by adjusting the molecular weight.

Specifically, the present invention provides the use of the cationic cellulose polymer for imparting flexibility to hair, skin, or fiber, the use for cumulatively adsorbing active ingredients onto hair, skin, or fiber by allowing the active ingredients to be bound to the cationic cellulose polymer, the use for transferring active ingredients to hair, skin, or fiber by allowing the active ingredients to be bound to the cationic cellulose polymer, and the use of the cationic cellulose polymer, a crosslinking-mediating component having a carboxyl group or amine group, and a carbodiimide-based compound for preventing the loss of hair, skin, or fiber components.

Claims

1. A composition for treating hair, skin, or fiber, comprising the polymer represented by Chemical Formula 1 below: ##STR00008## wherein n number of Q is each independently H or ##STR00009## but not all H, R.sub.1, R.sub.2, and R.sub.3 are each independently C.sub.1-6 alkyl, alkenyl, or alkynyl, m is an integer from 1 to 10, is H or OH; x is an integer from 1 to 100; n is an integer from 10 to 1000; and are each independently O(CH.sub.2CH.sub.2O).sub.sH, wherein s is an integer from 0 to 100; and wherein the molecular weight of the polymer is 10,000 to 4,000,000.

2. (canceled)

3. The composition of claim 1, wherein in the polymer, the ratio of n: the number of Q, when Q is ##STR00010## is 1:0.3 to 1:0.7, and the molecular weight of the polymer is 600,000 to 2,500,000.

4. (canceled)

5. The composition of claim 1, wherein the polymer is comprised in an amount of 0.01 to 10% by weight relative to the total weight of the composition.

6. The composition of claim 1, wherein the polymer provides the use for cumulatively adsorbing an active ingredient onto hair, skin, or fiber by allowing an OH group comprised in a, an OH group comprised in 13, or both to be bound to the active ingredient.

7. The composition of claim 6, wherein in the polymer, the ratio of n: the number of Q, when Q is ##STR00011## is 1:0.3 to 1:0.7, and the molecular weight of the polymer is 10,000 to 400,000.

8. The composition of claim 6, wherein the active ingredient is a reactive dye.

9. The composition of claim 8, wherein the reactive dye has a reactive group selected from dichlorotriazinyl, difluorochloro pyrimidine, monofluoro triazinyl, dichloroquinoxaline, vinyl sulfone, difluorotriazine, monochloro triazinyl, bromo acrylamide, and trichloropyrimidine.

10. The composition of claim 8, wherein the reactive dye comprises a chromophore selected from azo, anthraquinone, phthalocyanine, formazan, and tripendioxazine.

11. The composition of claim 6, further comprising an anionic surfactant.

12. The composition of claim 6, wherein the polymer is comprised in an amount of 0.01 to 1 wt % by weight relative to the total weight of the composition.

13. The composition of claim 1, wherein the polymer provides the use for transferring an active ingredient to hair, skin, or fiber by allowing an OH group comprised in , an OH group comprised in , or both to be bound to the active ingredient.

14. The composition of claim 13, wherein in the polymer, the ratio of n: the number of Q, when Q is ##STR00012## is 1:0.3 to 1:0.7, and the molecular weight of the polymer is 1,300,000 to 4,000,000.

15. (canceled)

16. (canceled)

17. (canceled)

18. (canceled)

19. The composition of claim 1, providing the use for preventing the loss of hair, skin, or fiber components by further comprising a carbodiimide-based compound and a crosslinking-mediating component having a carboxyl group or an amine group.

20. The composition of claim 19, wherein in the polymer, the ratio of n: the number of Q, when Q is ##STR00013## is 1:0.3 to 1:0.7, and the molecular weight of the polymer is 600,000 to 2,500,000.

21. The composition of claim 19, wherein the carbodiimide-based compound is a compound comprising an NCN structure.

22. The composition of claim 19, wherein the carbodiimide-based compound is selected from the group consisting of N,N-methylene-bis-(4-isocyanatocyclohexane)-, homopolymer, polyethylene glycol mono-Me-ether-blocked; N,N-dicyclohexylcarbodiimide; N,N-diisopropylcarbodiimide; N-ethyl-N(3-dimethylaminopropyl)carbodiimidehydrochloride; N-cyclohexyl,N-isopropylcarbodiimide; N-tert-butyl,N-methylcarbodiimide; N-tert-butyl,N-ethylcarbodiimide; N,N-dicyclopentylcarbodiimide; bis[[4-(2,2-dimethyl-1,3-dioxolye]methyl]carbodiimide; N-ethyl,N-phenylcarbodimide; N-phenyl,N-isopropylcarbodiimide; and derivatives thereof.

23. (canceled)

24. The composition of claim 19, further comprising a polar oil.

25. The composition of claim 24, wherein the polar oil is selected from the group consisting of isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2-octyldodecyl palmitate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, dicaprylyl carbonate (Cetiol CC), cocoglyceride (Myritol 331), butylene glycol dicaprylate/dicaprate, dibutyl adipate, and synthetic, semi-synthetic, plant, animal, and mineral natural mixtures of these esters, and has an interfacial tension of 150 mN/m or less.

26. (canceled)

27. The composition of claim 19, wherein the polymer is comprised in an amount of 0.01% to 10% by weight relative to the total weight of the composition.

28. A method for treating hair, skin, or fiber, using a polymer of claim 1, wherein the polymer imparts flexibility to the hair, skin, or fiber, wherein the polymer represented by Chemical Formula 1 below: ##STR00014## wherein n number of Q is each independently H or ##STR00015## but not all H, R.sub.1, R.sub.2, and R.sub.3 are each independently C.sub.1-6 alkyl, alkenyl, or alkynyl, m is an integer from 1 to 10, is H or OH; x is an integer from 1 to 100; n is an integer from 10 to 1000; and are each independently O(CH.sub.2CH.sub.2O).sub.sH, wherein s is an integer from 0 to 100; and wherein the molecular weight of the polymer is 10,000 to 4,000,000.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0195] FIG. 1 is a nanoscale image obtained by imaging the polymers of Comparative Example 8 and Example 2 with AFM.

[0196] FIG. 2 is a graph showing the film thicknesses of the polymers of Comparative Example 8 and Example 2 according to the number of adsorptions.

[0197] FIG. 3 shows numerical values obtained by evaluating the changes in adsorption thickness according to an increase in the rinsing power with AFM, illustrating values obtained by changing the adsorption condition of (A) Comparative Example 10 and (B) Example 2.

[0198] FIG. 4 is a graph showing the thickness of the polymer film adsorbed on mica by AFM according to the number of adsorptions. FIG. 4 (A) shows the thickness variation of Example 9, and FIG. 4 (B) shows the thickness variation of Comparative Example 23.

[0199] FIG. 5 is a confocal fluorescence microscope image. FIG. 5 (A) shows the bottom and top images of the adsorption layer of Example 9, and FIG. 5 (B) shows the bottom and top images of the adsorption layer of Comparative Example 23.

[0200] FIG. 6 is an image obtained by applying a dye to hair, and FIG. 6 (A) shows Example 9 and FIG. 6 (B) shows Comparative Example 23.

[0201] FIG. 7 is a nanoscale image of Comparative Example 25 obtained by imaging the polymer with AFM (XE-100, Park Systems, Korea). FIG. 7 (A) is an image at the time of AFM scanning, where the left side illustrates the polymer adsorption layer, and the right side illustrates the bottom of the mica disk as a substrate based on the boundary. The cantilever (NSC 36C, MikroMasch, Germany) measures the step between the polymer adsorption layer and the bottom of the mica disk. FIG. 7 (B) is an image with a z-axis resolution of 0.1 nm obtained through (A).

[0202] FIG. 8 is a graph showing the thickness of the adsorption layer according to the number of adsorptions. FIG. 8 (A) is a graph of Comparative Examples 25 to 27, and FIG. 8 (B) is a graph of Examples 11 to 13.

[0203] FIG. 9 is aa confocal fluorescence microscope image (LSM710, Carl Zeiss, Germany). FIG. 9 (A) is an image of Comparative Example 25, and FIG. 9 (B) is an image of Example 11, where the bottom illustrates the bottom image of the adsorption layer, and up illustrates the top image of the adsorption layer.

[0204] FIG. 10 is an image showing the results of using Comparative Example 25 (A) and Example 11 (B) for hair dyeing. The results obtained by using once, twice, and third time are shown in the order from left to right.

[0205] FIG. 11 is a schematic diagram showing the mechanism by which ingredients in the hair are lost by anionic surfactants. Group A shows components having low hydrophobicity or amphipathicity in the components of hair, and Group B shows components having hydrophobicity in the components of hair.

[0206] FIGS. 12 (A) and 12 (B) are graphs showing the values obtained by quantifying the loss of lipids in hair by gas chromatography according to washing in an embodiment of the present invention as a relative value (%) to untreated hair. Experimental groups 1 to 9 are as follows in the order below: C.sub.14. Myristyl acid, C.sub.16. Palmitic acid, C.sub.18. Stearic acid, C.sub.18=1:oleic acid, cholesterol, squalene, C.sub.14-C.sub.14 lipid, C.sub.14-C.sub.16 lipid, and C.sub.16-C.sub.16, C.sub.18-C.sub.16 lipid.

[0207] FIG. 13 is a graph showing the results of confirming the effect of preventing the loss of lipids in hair by treatment with the composition according to an embodiment of the present invention. Group A shows lipids having low hydrophobicity or amphipathicity in the components of hair, and Group B shows lipids having hydrophobicity in the components of hair.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0208] Hereinafter, the present invention will be described in detail by way of Examples to help understanding of the present invention. However, the Examples according to the present invention may be modified in various forms, and the scope of the present invention should not be interpreted as being limited thereto. These examples of the present invention are provided to more fully explain the invention to those having ordinary knowledge in the art to which the invention belongs.

1. Preparation of Cationic Polymer

[0209] In the following Examples and Comparative Examples, raw materials synthesized by the present inventors were used, and raw materials manufactured by the Dow Chemical Company were used as needed. The molecular weight was controlled by varying the content of ethyl cellulose in the polymerization process, and the nitrogen content was controlled by varying the amount of trimethylamine used to eventually control the amount of cationization degree.

[0210] A quaternized ammonium salt obtained by a quaternization reaction of hydroxyethyl cellulose with chlorohydroxypropyl trimethylamine was prepared. Specifically, sodium hydroxide and urea as solvents were added at a concentration in a weight ratio of 7.5:11:81.5 relative to water, and then, hydroxyethyl cellulose was dissolved therein at a concentration of 2% by weight. Thereafter, the quaternized ammonium-based compound was further added at an appropriate excess concentration (molar number of 3, 6, or 9 times relative to the glucose ring of cellulose) and the reaction was carried out according to temperature conditions (25, 45, or 60 C.) for modification to prepare a quaternized cationic cellulose polymer of Chemical Formula 1.

[0211] Further, referring to Reference Document (WO 2016085099 A1), EO addition or alkylation was carried out to prepare a structure including an alkyl group. Specifically, the addition of EU was carried out by proceeding gas-phase polymerization in order to introduce ethylene oxide (EO) to the and positions in the glucose ring of the cationic cellulose polymer using an epoxide, spraying the reactants in the chamber thereto, and then proceeding a reaction by applying temperature and pressure. In the case of alkylation, the reaction was carried out using reactants having a halohydrin, aldehyde, or epoxide functional group at the end so as to introduce a desired alkyl group, and as a result, the OH groups at the and positions in the glucose ring were substituted with alkyl.

2. Property of Imparting Flexibility to Hair, Skin, or Fiber of Cationic Polymer

(1) Change in Thickness of Cumulative Adsorption According to Substituents at and Positions During Polymer Adsorption

[0212] In order to confirm the cumulative adsorption characteristics of polymers and the impact of rinsing power on the polymers according to the substituent groups at the and positions in the glucose ring of the cationic polymer, polymer samples of Examples and Comparative Examples in which C2 () and C3 () were substituted in the glucose ring were prepared, as shown in Table 1. In Comparative Example 1, distilled water was used as a control group. The cationic cellulose polymers of Examples and Comparative Examples were synthesized with a molecular weight of 800,000 and a nitrogen content (% by weight) of 2.7% by weight. Table 1 below shows substitution positions and substituent groups.

TABLE-US-00001 TABLE 1 Comparative Comparative Samples Example 1 Example 2 Example 3 Example 2 Example 3 Substitution Substituent EO OH Divalent OH Divalent Monovalent OH OH Alkyl OH Groups or or or higher having higher higher valent C5 EO valent EO or less EO Comparative Comparative Comparative Comparative Samples Example 4 Example 5 Example 6 Example 7 Substitution Substituent Alkyl OH Alkyl OH Alkyl OH Quaternized EO Groups having having having ammonium C5 C10 C18 or OR OR more more more and and C10 C18 or less or less

[0213] In order to evaluate the adsorption state of cationic polymers, mica, which has a Zeta potential of tens of mV, generally similar to that of hair and wool, was selected as the substrate using the method practiced by many companies including Dow Corning, a raw-material manufacturing company for conditioning agents, and the cationic polymers were adsorbed onto the mica substrate to determine the adsorption characteristics of the polymers. Since there exist many variables such as an interval between hair cuticles, cuticle thickness, cuticle state, hair hydrophobicity, hair thicknesses, etc. for each hair even within the same person, the method of comparing the cationic polymers by directly adsorbing the same onto the hair cannot be a proper evaluation method. Therefore, in this experiment, cumulative adsorption was evaluated by selecting mica discs as a substrate and measuring the adsorption thickness of the cationic polymers.

[0214] 12 mm diameter mica discs (TED PELLA, Canada) were used as an adsorbent. The polymers were placed and adsorbed onto only half of the mica discs using 10 ml of distilled water containing 0.5% of polymers, and then placed and washed with distilled water. The amount of polymer adsorption is determined by the electrical attraction and repulsion between the polymers, the mica, and the polymers adsorbed onto the mica. Since the desorption proceeds due to the hydrophilicity of the polymers and water, the change in the polymer content is not a factor affecting the adsorption amount. Therefore, the polymer content of 0.5% commonly used in the shampoo was selected as an experimental condition.

[0215] The interface between the adsorbed polymer layer and the mica bottom was observed by the atomic force microscopy (AFM, Model Systems XE-100, Korea) using the topography of the contact mode of the tip (NSC 36C, Mikro Masch, Germany), and the thickness thereof was evaluated as shown in FIG. 1, and the average thickness is shown in Table 2.

[0216] Comparative Example 1 in Table 2 shows the measured values of the thickness of mica immersed only in distilled water containing no polymer. As can be seen from the results of Comparative Example 1, the cumulative adsorption is resulted from the polymer adsorption, and the thickness difference is resulted from the difference in the polymer adsorption amount.

[0217] Comparative Example 2 is a cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7% by weight, wherein is an OH group and is an OH group in the Chemical Formula 1, and Comparative Example 3 is a cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7% by weight, wherein is an alkyl group having 5 carbon atoms or less and is an OH group in the Chemical Formula 1.

[0218] Comparative Example 4 is a cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7% by weight, wherein is an alkyl group having 5 to 10 carbon atoms and is an OH group in the Chemical Formula 1, and Comparative Example 5 is a cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7% by weight, wherein is an alkyl group having 10 to 18 carbon atoms, and is an OH group in the Chemical Formula 1.

[0219] Comparative Example 6 is a cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7% by weight, wherein is an alkyl group having 18 or more carbon atoms and is an OH group in the Chemical Formula 1, and Comparative Example 7 is a cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7% by weight, wherein is a quaternized ammonium and is an OH group in the Chemical Formula 1, wherein the quaternized ammonium is the same as the quaternized ammonium connected to the ethylene oxide (EO) group of the glucose ring C5 of the Chemical Formula 1.

[0220] Example 1 is a cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7% by weight, wherein is an ethylene oxide (EO) group and is an OH group in the Chemical Formula 1, and Example 2 is a cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7% by weight, wherein is a divalent or higher valent ethylene oxide (EU) group and is an OH group in the Chemical Formula 1.

[0221] Example 3 is a cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7% by weight, wherein is a divalent or higher valent ethylene oxide (EO) group and is a monovalent or higher valent EO group in the Chemical Formula 1. Table 2 shows thickness measurements according to polymer conversion (unit: m).

TABLE-US-00002 TABLE 2 Number of Example Example Example Comparative Comparative Comparative Comparative Comparative Comparative Comparative adsorptions 1 2 3 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 0 0 0 0 0 0 0 0 0 0 0 1 0.562 0.525 0.538 0 0.583 0.635 0.682 0.735 0.625 0.373 2 0.672 0.620 0.622 0 0.682 0.748 0.713 0.815 0.735 0.367 3 0.725 0.447 0.527 0 0.692 0.945 0.824 0.863 0.795 0.318 4 0.430 0.378 0.374 0 0.726 1.133 0.924 0.928 0.835 0.283 5 0.472 0.358 0.346 0 0.801 1.285 1.015 1.139 0.935 0.273 6 0.452 0.374 0.348 0 0.840 1.428 1.215 1.257 1.015 0.235 7 0.448 0.387 0.350 0 0.834 1.623 1.368 1.367 1.213 0.231 8 0.428 0.389 0.342 0 0.883 1.932 1.626 1.547 1.254 0.217 9 0.463 0.391 0.347 0 0.892 2.045 1.935 1.782 1.269 0.169 10 0.438 0.381 0.362 0 0.902 2.153 2.035 1.824 1.330 0.105 11 0.452 0.378 0.360 0 0.937 2.326 2.386 1.946 1.394 0.061

[0222] From the results shown in Table 2, it can be seen that the thicknesses adsorbed in Examples 1 to 3 were constant. From this, it can be seen that the effect of preventing cumulative adsorption was exhibited when EO was added to carbon 2 or 3 of the glucose ring unit in the cellulose skeleton.

[0223] In the above Examples, the thickness of the adsorption layer increased during repeated adsorption from one to three times, implying that the cationic polymers were steadily adsorbed as a single layer onto the space above the negatively charged surface. The adsorption thickness of the cation polymers decreased from 3 and 4 times of adsorption, indicating that the anionic surface was fully covered by the adsorption of the cation polymers. When the cationic polymers were adsorbed onto a single layer having an overall negative charge, the adsorption force was reduced due to the cationic repulsive force with the already adsorbed polymers. Therefore, the polymers of the adsorption layer on the single layer were washed away by the hydrophilic force with water in the rinsing process.

[0224] In Comparative Examples 2 to 6, it was observed that the adsorption thickness of the adsorption layer was increased as the number of adsorptions was increased. Considering that the degree of cationization was similar compared to those of Examples 1 to 3, although the adsorption layer and the cationic polymer had a similar cationic repulsive force therebetween, it seems that the cumulative adsorption was proceeded with relatively reduced rinsing power with respect to the bonding relationship with water. In fact, it can be seen that the hydrophobicity increased as the length of the alkyl group increased, thereby reducing the hydrophilic force with water molecules, resulting in a cumulative adsorption phenomenon.

[0225] In Comparative Example 7, it can be seen that the thickness of the adsorption layer was remarkably reduced as the number of adsorptions increased. This may be illustrated as a phenomenon in which the cationic polymers adsorbed in the rinsing process after the polymer has been adsorbed onto the surface of the hair was washed away by binding to water molecules. That is, when two or more ammonium were present in the quaternized cellulose, the rinsing power was excessively increased, thereby preventing the adsorption of the polymer.

(2) Change in Thickness of Cumulative Adsorption Layer According to Molecular Weight and Degree of Cationization During Polymer Adsorption

[0226] In order to confirm the effect of the molecular weight on the adsorption characteristics of the cationic polymer, polymer samples of Examples and Comparative Examples having molecular weights and nitrogen contents (% by weight) as shown in Table 3 below were prepared. In Comparative Example 8, a Ucare polymer JR125 manufactured by the Dow Chemical Company was used, and the polymer of Comparative Example 9 was prepared. As the polymer of Comparative Example 10, a Ucare polymer JR30M manufactured by the Dow Chemical Company was used, and the polymers of Comparative Examples 11 to 14 were prepared. Table 3 below shows samples for evaluation of the thickness of cumulative adsorption layers.

TABLE-US-00003 TABLE 3 Example Example Example Comparative Comparative Comparative Comparative Comparative Comparative Comparative Samples 2 4 5 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Polymer Cellulose Cellulose Cellulose Cellulose Cellulose Cellulose Cellulose Cellulose Cellulose Cellulose Molecular 800,000 1,800,000 2,500,000 250,000 250,000 800,000 1,800,000 2,500,000 3,000,000 3,000,000 Weight N % 2.7 2.7 2.7 1.8 2.7 1.8 1.8 1.8 1.8 2.7

[0227] In Comparative Example 8, a cationic cellulose polymer having a molecular weight of 250,000 and a nitrogen content of 1.8% by weight was used, and in Comparative Example 9, a cationic cellulose polymer having a molecular weight of 250,000 and a nitrogen content of 2.7% by weight was used

[0228] In Comparative Example 10, a cationic cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 1.8% by weight was used, and in Comparative Example 11, a cationic cellulose polymer having a molecular weight of 1,800,000 and a nitrogen content of 1.8% by weight was used.

[0229] In Comparative Example 12, a cationic cellulose polymer having a molecular weight of 2,500,000 and a nitrogen content of 1.8% by weight was used, and in Comparative Example 13, a cationic cellulose polymer having a molecular weight of 3,000,000 and a nitrogen content of 1.8% by weight was used.

[0230] In Comparative Example 14, a cationic cellulose polymer having a molecular weight of 3,000,000 and a nitrogen content of 2.7% by weight was used, and in Example 2, a cationic cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7% by weight was used.

[0231] In Example 4, a cationic cellulose polymer having a molecular weight of 1,800,000 and a nitrogen content of 2.7% by weight was used, and in Example 5, a cationic cellulose polymer having a molecular weight of 2,500,000 and a nitrogen content of 2.7% by weight was used. Table 4 below shows the results of evaluating the thickness of cumulative adsorption layers (unit: m).

TABLE-US-00004 TABLE 4 Number of Example Example Example Comparative Comparative Comparative Comparative Comparative Comparative Comparative adsorptions 2 4 5 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 0 0 0 0 0 0 0 0 0 0 0 1 0.525 0.552 0.589 0.253 0.385 0.363 0.743 0.737 0.933 1.291 2 0.620 0.783 0.843 0.327 0.483 0.473 0.528 0.748 0.982 1.425 3 0.378 0.483 0.503 0.527 0.627 0.663 0.835 0.964 1.067 1.283 4 0.378 0.419 0.479 0.592 0.593 0.730 0.725 1.089 1.263 1.532 5 0.358 0.485 0.495 0.683 0.705 0.873 1.356 1.125 1.472 1.853 6 0.374 0.483 0.467 0.795 0.864 0.948 1.632 1.236 1.628 1.902 7 0.387 0.538 0.519 0.877 0.935 1.048 1.853 1.467 1.836 2.105 8 0.389 0.513 0.506 0.963 0.864 1.294 2.033 1.774 1.929 2.075 9 0.391 0.496 0.542 1.043 0.926 1.385 2.185 2.086 2.148 2.532 10 0.381 0.551 0.553 1.142 1.426 1.492 2.532 2.332 2.436 2.938 11 0.378 0.527 0.548 1.204 1.583 1.585 2.963 2.406 2.839 3.502

[0232] From the results shown in Table 4, it can be seen that the adsorbed thicknesses in Example 2 and Examples 4 and 5 were constant. It can be confirmed therefrom that the cumulative adsorption phenomenon could be prevented by adjusting the molecular weight and the nitrogen content (degree of cationization). Further, it was confirmed from the Comparative Examples 8 to 14 that the adsorption thickness increased when the number of adsorptions of the polymer was increased (FIGS. 1 and 2).

[0233] It seems that when adsorbed onto the surface of the anionic hair, the polymers, due to the high degree of cationization, were uniformly adsorbed in a constant amount. In fact, in the Examples except Example 2 and Examples 4 and 5, the cases in which the thickness layer of the polymers was not uniform were also observed. In the Examples, it seems that the increase in the adsorption thickness when adsorption was carried out for 1 to 2 times attributes to the continued adsorption of the cationic polymers on the hair surface. From the third time of the adsorption, the thickness decreased and became uniform, and the adsorption was prevented by the mutual electric repulsive force between the cationic polymer layer adsorbed onto the hair and the cationic polymers to be adsorbed. Meanwhile, the portion onto which the polymer was adsorbed in a constant amount due to the molecular weight was formed, as the polymer adsorption layer with a high degree of cationization had hydrophilicity and was bound to water molecules, and washed away in the rinsing process. As a result, it seems that the cumulative adsorption phenomenon was prevented when the conditions of cellulose molecular weight in the range of 800,000 to 2,500,000 and nitrogen content of 2.7% by weight of Example 2 and Examples 4 to 5 were applied.

(3) Change in Thickness of Cumulative Adsorption Layer According to Rinsing Power

[0234] In order to confirm whether the phenomenon of the cumulative adsorption prevention shown in Table 4 was caused by the rinsing power, and an experiment was conducted to confirm the adsorption thickness by changing the rinsing power, while polymer adsorption was conducted as shown in Table 5 under the adsorption conditions of Comparative Example 10 and Example 2. In the cases of Comparative Example 10 and Example 2, the molecular weight of each polymer was the same as 800,000, but their nitrogen content was different, which was 1.8 and 2.7% by weight, respectively. Table 5 below shows samples for evaluating the thickness of cumulative adsorption layers.

TABLE-US-00005 TABLE 5 Experimental Experiment Experiment Experiment Experiment Experiment Experiment Experiment Experiment Category #1 #2 #3 #4 #5 #6 #7 #8 Nitrogen 1.8% 1.8% 1.8% 1.8% 2.7% 2.7% 2.7% 2.7% Content (Comparative (Comparative (Comparative (Comparative (Example 2) (Example 2) (Example 2) (Example 2) Example 10 Example 10 Example 10) Example 10) rpm 0 20 40 60 0 20 40 60

[0235] Experiments #1 to #4 were performed with the polymer of Comparative Example 10, and Experiments #5 to #8 were performed with the polymer of Example 2. All experiments were carried out as follows: the polymers were adsorbed onto the mica discs, placed thereon, and then washed, and subsequently, each Petri dish was added to a shaker (Jeio Tech, SI-900R, Korea) and shaken at 20, 40, and 60 rpm to exhibit rinsing power. After varying the rinsing power, the thickness of the adsorption layer was measured and shown as in Table 6.

TABLE-US-00006 TABLE 6 Experimental Experiment Experiment Experiment Experiment Experiment Experiment Experiment Experiment Category #1 #2 #3 #4 #5 #6 #7 #8 0 0 0 0 0 0 0 0 0 1 0.335 0.315 0.351 0.421 0.525 0.453 0.402 0.352 2 0.521 0.521 0.583 0.482 0.620 0.513 0.452 0.423 3 0.663 0.692 0.678 0.613 0.447 0.392 0.358 0.317 4 0.801 0.731 0.752 0.714 0.378 0.341 0.309 0.271 5 0.873 0.862 0.898 0.811 0.358 0.331 0.308 0.261 6 1.024 0.972 0.942 0.936 0.374 0.325 0.305 0.285 7 1.048 0.992 1.032 1.154 0.387 0.352 0.318 0.285 8 1.294 1.236 1.262 1.248 0.389 0.359 0.308 0.278 9 1.325 1.392 1.402 1.346 0.391 0.342 0.308 0.274 10 1.492 1.493 1.457 1.438 0.381 0.343 0.319 0.285 11 1.585 1.502 1.544 1.526 0.378 0.351 0.301 0.294

[0236] The thickness variations in Table 6 are shown as a graph in FIG. 3. FIG. 3 (A) shows the result of Experiment #1 to Experiment #4, and FIG. 3 (B) shows the result of Experiment #5 to Experiment #8. When (A), which has a relatively low nitrogen content, was compared to (B), which has a high nitrogen content, cumulative adsorption occurred. In this case, there was no variation of the adsorption thickness even when the rinsing power was increased. However, in the case where the cumulative adsorption was prevented as shown in (B), the adsorption thickness was decreased and thus varied with an increase in the rinsing power.

[0237] From the above results, it can be seen that the phenomenon of cumulative adsorption prevention of the adsorption layer was associated with the high-nitrogen polymer, and the high degree cationization, which reflects the high-nitrogen portion, and the hydrophilicity acting on the water play a crucial role in providing such effect.

[0238] That is, it was found that the cumulative adsorption phenomenon could be prevented by adsorbing polymers having a high nitrogen content in order to utilize the rinsing power. In other words, the adsorption of polymers having a high nitrogen content was proved to be effective in preventing cumulative adsorption by hydrophilicity

(4) Change in Thickness of Cumulative Adsorption Layer According to Degree of Cationization During Polymer Adsorption

[0239] Since it was confirmed that cumulative adsorption did not occur in Example 2 and Examples 4 and 5 of Table 3, polymers were prepared by variously applying the degree of cationization based on the molecular weight of 800,000 of the cationic polymer of Example 2 as shown in Table 7. The degree of cationization is determined by the nitrogen content. Table 7 below shows samples for evaluating the thickness of cumulative adsorption layer according to the degree of cationization.

TABLE-US-00007 TABLE 7 Compar- Compar- Compar- Example Example ative ative ative Samples 6 7 Example 15 Example 16 Example 17 Polymer Cellulose Cellulose Cellulose Cellulose Cellulose Molec- 800,000 800,000 800,000 800,000 800,000 ular Weight N % 2.3 3.0 1.7 2.0 3.3

[0240] With respect to the samples of Table 7, the evaluation of adsorption thickness was carried out according to the degree of cationization, and the results are shown in Table 8 below (unit: m).

TABLE-US-00008 TABLE 8 Number of Example Example Comparative Comparative Comparative Comparative adsorptions 6 7 Example 10 Example 15 Example 16 Example 17 0 0 0 0 0 0 0 1 0.453 0.463 0.363 0.438 0.427 0.478 2 0.648 0.436 0.473 0.502 0.453 0.592 3 0.683 0.437 0.663 0.581 0.464 0.482 4 0.437 0.410 0.730 0.627 0.502 0.412 5 0.378 0.408 0.873 0.653 0.489 0.403 6 0.354 0.431 0.948 0.684 0.517 0.382 7 0.387 0.420 1.048 0.699 0.537 0.371 8 0.348 0.397 1.294 0.753 0.583 0.352 9 0.349 0.392 1.385 0.799 0.573 0.321 10 0.338 0.441 1.492 0.831 0.628 0.296 11 0.376 0.404 1.585 0.863 0.649 0.269

[0241] As shown in Table 8, in the case of Comparative Example 10, Comparative Examples 15 and 16, the adsorption thickness increased with an increase in the number of adsorptions, and thus, it can be seen that the cumulative adsorption phenomenon occurred because the degree of cationization due to the electric repulsive force generated during the adsorption described above was insufficient.

[0242] In the cases of Examples 6 to 7, no increase in adsorption thickness according to an increase in the number of adsorptions was observed, and it was confirmed that cumulative adsorption was prevented when the nitrogen content was in a range of 2.3 to 3.2% by weight while the molecular weight was 800,000. It can be seen therefrom that, in the case of a low molecular weight, the additional adsorption could be suppressed by the electric repulsive force only when the degree of cationization reaches a certain level.

[0243] However, in the case of Comparative Example 17 in which the nitrogen content determining the degree of cationization was higher than 3.2% by weight based on the weight of the polymer, although the cumulative adsorption phenomenon was prevented, the adsorption layer was rather decreased as the number of adsorptions increased, resulting in the interference with the amount of adsorption which imparts a conditioning effect. Accordingly, it was determined that desorption resulted from hydrophilicity with water in the rinsing process due to a high degree of cationization.

(5) Change in Thickness of Cumulative Adsorption Layer According to Polymer Base During Polymer Adsorption

[0244] For the evaluation of the thickness of the cumulative adsorption layer according to polymer bases, the cumulative adsorption phenomenon was observed with respect to the cellulose and other polymers shown in Table 9 below, and the results are shown in Table 10 below.

[0245] In Comparative Example 18, N-Hance CCG45 manufactured by Ashland, a guar hydroxypropyltrimonium chloride, was used. In Comparative Example 19, OaSense Care CT400 manufactured by Ashland, a hydroxypropyl guar hydroxypropyltrimonium chloride, was used.

[0246] In Comparative Examples 20 and 21, a synthetic polymer of ethyltrimonium chloride methacrylate/propyltrimonium acrylamide/dimethylacrylamide copolymer of KR Patent No. 10-1291693 was used. Table 9 below shows samples for evaluating the cumulative adsorption through the polymer bases.

TABLE-US-00009 TABLE 9 Comparative Comparative Comparative Comparative Samples Example 18 Example 19 Example 20 Example 21 Polymer Guar Guar Synthetic Synthetic Molecular 800,000 800,000 800,000 800,000 Weight N % 1.4 2.7 1.4 2.7

[0247] Table 10 below shows the results of cumulative adsorption evaluation for the samples of Table 9 (unit: m).

TABLE-US-00010 TABLE 10 Number of Comparative Comparative Comparative Comparative adsorptions Example 18 Example 19 Example 20 Example 21 0 0 0 0 0 1 0.935 1.027 0.673 0.783 2 1.025 1.453 0.693 0.892 3 1.284 1.364 0.783 0.904 4 1.257 1.502 0.893 0.978 5 1.563 1.789 0.834 1.025 6 1.375 1.853 0.904 1.064 7 1.694 1.762 1.024 1.194 8 1.792 1.981 1.083 1.285 9 1.802 1.972 1.184 1.304 10 1.894 2.247 1.283 1.503 11 2.005 2.283 1.306 1.603

[0248] As shown in Table 10, no phenomenon of cumulative adsorption prevention was observed in the polymers other than cellulose. This is because the chemical structure of the cellulose has a linear ethyl cellulose structure, while the guar polymer has a branched structure, and accordingly, in the guar polymers, the desorption effect, which occurs during rinsing, was remarkedly reduced due to the hydrophilicity after adsorption, thus failing to prevent the cumulative adsorption phenomenon. In the case of the synthetic polymers, it is interpreted that the repulsive force during adsorption was different from that of cellulose due to the difference in the bonding position of the cationic nitrogen.

(6) Sensory Evaluation of Rinsing and Conditioning According to Polymer

[0249] The shampoo compositions were prepared in a conventional manner according to the prescription shown in Table 11 below.

TABLE-US-00011 TABLE 11 Mixing Ingredients Weight Ratio (%) Polymer 0.5 Sodium laureth sulfate 8 Cocamidopropyl betaine 4.5 EDTA 4Na, citric acid monohydrate 0.1 Other ingredients 16 Purified water Residual amount (to 100)

[0250] Since cellulose-based polymers have excellent solubility, after adding the polymers, surfactants were added in sequence and dissolved and then the pH was neutralized by adding EDTA.4Na and citric acid monohydrate. As other ingredients, preservatives, fragrances, dispersants, viscosity modifiers, and pH modifiers were added.

[0251] 1 g of hair tress was added to 100 mL of a 10% diluted shampoo solution and stirred for 5 minutes at 150 rpm and then rinsed for 2 minutes with a flow rate of 4 ml/sec, and this whole process was repeated 5 times. Sensory evaluation was performed to evaluate the stiffness of the treated hair, and the results are shown in Table 12 below. The experiment was conducted on 15 male and 15 female subjects, and they were required to evaluate the conditioning effect of the hair after shampooing based on the evaluation criteria of freshness. The results are shown in Table 12 below as average values.

[0252] Experiment #9 was the result of treatment with sodium lauryl sulfate, an anionic surfactant, without the treatment of any polymer, and Experiment #10 was treated with the hair in which the cumulative adsorption phenomenon occurred after shampooing using the cationic cellulose polymer of Comparative Example 10. Additionally, in Experiment #11, the polymer according to the present invention (Example 2) was applied as a conditioning polymer.

[0253] Evaluation CriteriaThe order of hair freshness was measured, and the opposite represents roughness.

[0254] (5: Very good); (4: Good); (3: Moderate); (2: Bad); (1: Very bad)

TABLE-US-00012 TABLE 12 Experiment Experiment Experiment Experimental Category #9 #10 #11 When wet 1.3 1.9 3.7 After drying 2.1 1.6 4.2

[0255] As shown in Experiment #11 of Table 12, it can be seen that the polymer in which the cumulative adsorption was prevented provided freshness and was escaping from providing the sense of stiffness.

(7) Evaluation of Frictional Force

[0256] The conditioning effect of the cationic polymer was applied to shampoo, and the frictional force was quantified by device evaluation.

[0257] The shampoo composition of Table 11 was added to the burex hair tress in an amount of 10% by weight, and the hair was lathered for 15 seconds, rubbed for 20 seconds, rinsed for 15 seconds with running water at 37 C., wiped with a towel to remove moisture, and then evaluated for the frictional force using an MTT 175 Miniature Tensile Tester (Diastron, GB).

[0258] The other hair treated with the shampoo was rinsed for 2 minutes and then dried with a dryer for 2 minutes, and was maintained at a temperature of 25 C. in a constant temperature and humidity chamber under a condition of 50% humidity for one day, so that the moisture in the hair was kept constant. Thereafter, the frictional force was measured in the same temperature and humidity chamber and the results are shown in Table 13 below.

[0259] Herein, the hair tress was washed with sodium lauryl sulfate, an anionic surfactant, which was used as a reference value, and the value of the frictional force of the hair was calculated by comparing the difference from the corresponding measured value based thereon.

TABLE-US-00013 TABLE 13 Experiment #12 Experimental (Polymer of Comparative Experiment #13 Category Example) (Polymer of Example 2) During rinsing 21 55 After drying 13 21

[0260] From the results of Table 13, the shampoo, to which the polymer presented in the present invention was applied, showed reduced rinsing time during rinsing, and the frictional force was remarkably reduced even after drying, thereby improving the smooth conditioning effect. In addition, as can be seen from the above Examples, the polymer prepared in the present invention imparts the effect of preventing cumulative adsorption when applied as a conditioning agent, thereby overcoming the problem of the cumulative adsorption that gives a feeling of stiffness, and accordingly, it was confirmed that it provides freshness to the hair and is an excellent component for hair conditioning cosmetic compositions.

[0261] Subsequently, in order to confirm whether the phenomenon of cumulative adsorption prevention due to repeated use was applied to the hair, and at the same time, whether the stiffness caused by the accumulation prevention phenomenon was improved, the shampoo composition was treated 60 times to evaluate the frictional force as shown in Table 14.

TABLE-US-00014 TABLE 14 Experiment #14 Experimental (Polymer of Comparative Experiment #15 Category Example) (Polymer of Example 2) During rinsing 20 56 After drying 4 21

[0262] The decrease of the change in the frictional force on the hair surface in Experiment #14, which occurs when the shampoo according to the prescription of Table 11 was repeatedly applied for washing of the hair, can be understood as a decrease in the degree of smoothness due to the texture of the polymer accumulated in the hair when the shampoo is repeatedly used. In Experiment #15, the effect of no change in the frictional force even after repeated washing and adsorption reflects that there is no change in the polymer layer.

3. Property of Cumulatively Adsorbing Active Ingredients of Cationic Polymer, to which the Active Ingredients are Bound, onto Hair, Skin, or Fiber

(1) Preparation of Cationic Polymer to which Hair Dye is Bound

[0263] Cationic cellulose polymers were prepared according to the above-mentioned 1.

[0264] One of the reactive blue No. 4 dye and 5-([4,6-dichlorotriazin-2-yl]amino) fluorescein was selected and allowed to bind to the carbon atom at position 2 of the glucose monomer as shown in Reaction Schemes 1 and 2 below. The dyes can be used as a phosphor and a hair dye, and thus can grasp the polymer adsorption position of the active ingredient and utilize the dye function at the same time. In the reactive blue dye No. 4, both the fluorescence emission color and the visible light reflection color are blue, whereas in 5-([4,6-dichlorotriazin-2-yl]amino) fluorescein, the fluorescence emission color is green but it takes on a bright reddish orange color under the visible light.

##STR00005##

[0265] As a preparation method, the pH was lowered using KOH, and the dye was stirred with the polymer at 500 rpm, filtered with HPLC-grade ethanol, and then subjected to freeze-drying (Bondiro, Ilshin) for one week. However, as shown in Reaction Scheme 2, a binding between the amine group of the polymer and the carboxyl group of 5-([4,6-dichlorotriazin-2-yl]amino) fluorescein may occur, leading to aggregation. In this case, the aggregate can be decomposed by stirring with a homo mixer, if necessary.

(2) Change in Thickness of Adsorption Layer According to Viscosity and Molecular Weight

[0266] In order to evaluate the adsorption state of the cationic polymer bound with reactive blue No. 4, mica, which has a Zeta potential of tens of mV, similar to that of hair and wool, was selected as the substrate, and the cationic polymers were adsorbed onto the mica substrate to determine the adsorption characteristics of the polymers, using the method practiced by many companies including Dow Corning, a raw-material manufacturing company for conditioning agents.

[0267] 12 mm diameter mica discs (TED PELLA, Canada) were used as an adsorbent. The polymers were placed and adsorbed onto only half of the mica discs using 10 ml of distilled water containing 0.5% of each polymer, and then washed with distilled water. The amount of polymer adsorption is determined by the electrical attraction and repulsion between the polymer, the mica, and the polymer adsorbed onto the mica. Since the desorption proceeds due to the hydrophilicity between the polymer and water, the change in the polymer content is not a factor affecting the adsorption amount. Therefore, the polymer content of 0.5% commonly used in the shampoo was selected as an experimental condition.

[0268] The interface between the adsorbed polymer layer and the mica bottom was observed by the atomic force microscopy (AFM, Model Systems XE-100, Korea) using the topography of the contact mode of the tip, and the result of evaluating the thickness is shown in FIG. 1.

[0269] Examples 8 to 10 and Comparative Examples 22 to 24 having the viscosity of Table 15 were prepared for thickness variation experiments according to viscosity and molecular weight of the polymers.

TABLE-US-00015 TABLE 15 Comparative Comparative Comparative Samples Example 8 Example 9 Example 10 Example 22 Example 23 Example 24 Viscosity 50 200 500 600 700 800 (2%) Molecular 100,000 200,000 300,000 500,000 700,000 900,000 Weight

[0270] Table 16 shows the change in the thickness of adsorption layer according to the molecular weight of the polymers.

TABLE-US-00016 TABLE 16 Number of Comparative Comparative Comparative adsorptions Example 8 Example 9 Example 10 Example 22 Example 23 Example 24 0 0 0 0 0 0 0 1 0.32 0.18 0.19 0.52 0.68 0.69 3 0.72 0.51 0.36 0.37 0.40 0.42 5 0.82 0.76 0.46 0.35 0.37 0.39 7 0.92 0.82 0.52 0.38 0.38 0.40 9 1.01 0.87 0.58 0.37 0.42 0.41 11 1.10 0.93 0.64 0.38 0.37 0.40 13 1.14 1.02 0.74 0.37 0.38 0.41 15 1.21 1.13 0.83 0.40 0.39 0.39 17 1.26 1.22 0.92 0.39 0.41 0.40 (unit: m)

[0271] From the results shown in Table 16 and FIG. 4, in Examples 8 to 10 relating to the polymers having a viscosity of 50 to 500 in an aqueous solution state and a molecular weight of 100,000 to 300,000, it can be seen that the thickness of the polymers being adsorbed increased with additional adsorption.

[0272] In Comparative Examples 22 to 24, as the number of adsorptions increased, the adsorption thickness of the adsorption layer remained constant, and accordingly, it appears that the additional adsorption was not proceeded by the cationic repulsive force between the adsorption layer and the cation polymer, and the rinsing power with respect to the binding relationship with water.

(3) Analysis of Adsorption Layer Components Using Confocal Fluorescence Microscopy

[0273] After finding out that the polymer adsorption patterns can be divided into three types as seen in the results of Table 16 above, the confocal fluorescence microscopy was used to confirm as to why such variation phenomenon occurred.

[0274] A cellulose polymer bound with a fluorescent dye was examined using a confocal fluorescence microscope (Carl Zeiss, LSM710). With respect to the polymers of Example 9 and Comparative Example 23, the polymer bound with the reactive blue No. 4 dye was first adsorbed onto mica discs and washed three times, and subsequently, the polymer bound with the green fluorescent dye (5-([4,6-dichlorotriazin-2-yl]amino) fluorescein) was continuously adsorbed onto the mica discs and washed. A light laser with an excitation light wavelength of 420 nm and 510 nm was irradiated thereto, and the fluorescence spectrum was mapped onto the bottom with an area of 100 m100 m. Then, the first top part and the bottom part of the fluorescence spectrum were focused and mapped as shown in FIG. 5.

[0275] As shown in FIG. 5 (A), the polymer of Example 9 had a blue bottom, but no green color was detected. However, the blue fluorescent polymer was not detected at the top part, but only the green part was detected. That is, considering that the green-bound polymer was cumulatively adsorbed onto the blue-bound polymer, it is suggested that the cumulative adsorption was continuously carried out on the conventional adsorption layer whenever the polymer was adsorbed.

[0276] The polymer of Comparative Example 23 is shown in FIG. 5 (B). Only the blue fluorescent polymer was detected at both the top and bottom parts, and the green fluorescent polymer was not detected. This implies that the there was no further adsorption after the adsorption of the blue polymer was proceeded.

(4) Application of Accumulation Phenomenon to Hair

[0277] It was confirmed whether the variation phenomenon occurs after polymer adsorption by simultaneously applying an anionic surfactant-based shampoo to the hair, which is an actual biological substrate as shown in FIG. 6.

[0278] The shampoo composition was prepared in a conventional manner according to the prescription shown in Table 17 below.

TABLE-US-00017 TABLE 17 Mixing Components Weight ratio (%) Jojoba oil 0.1 Polymer 0.5 Sodium laureth sulfate 8 Cocamidopropyl betaine 4.5 EDTA 4Na, citric acid monohydrate 0.1 Other ingredients 16 Purified water Residual amount (to 100)

[0279] Since cellulose-based polymers have excellent solubility, after adding the polymers, surfactants were added in sequence and dissolved and then the pH was neutralized by adding EDTA.4Na and citric acid monohydrate. As other ingredients, preservatives, fragrances, dispersants, viscosity modifiers, and pH modifiers were added.

[0280] 1 g of hair tress was treated with the shampoo for 50 seconds and rinsed for 2 minutes with a flow rate of 4 ml/sec. FIGS. 3 1), 2), and 3) are the results of washing after a single treatment, two-repeated treatments, and three-repeated treatments, respectively.

[0281] In the case of the polymer of Example 9 in which adsorption proceeded according to the number of adsorptions, the hair color was strengthened depending on the dye color as the number of treatments increased as shown in FIG. 6 (A). In contrast, in the case of the polymer of Comparative Example 23 in which further adsorption was prevented, the polymer constantly appeared in blue, which was the first dye color, regardless of additional dyeing as shown in FIG. 6 (B).

[0282] Through the above Examples, it can be seen that the dyeing was actually strengthened when the polymer was applied to hair.

[0283] Table 18 shows the results of treating hair with the shampoo prepared using the polymer having a viscosity of 200 cps used in Example 9 to which the reactive blue No. 4 dye was bound, and the polymer having a viscosity of 700 cps used in Comparative Example 23, to which the reactive blue No. 4 dye was bound, as shown in Table 17, and the results of color change are expressed as a CIE lab value through a color difference meter.

TABLE-US-00018 TABLE 18 Example 9 Comparative Example 23 Samples Blue Green Yellow Blue Green Yellow 1 1.25 1.13 0.64 1.35 1.21 0.53 3 1.53 1.25 0.73 1.28 1.02 0.54 5 1.59 1.29 0.79 1.15 1.12 0.56 7 1.63 1.35 0.84 1.29 1.07 0.49 9 1.75 1.42 0.86 1.32 1.10 0.53

[0284] Color difference value, E=(L.sup.2+a.sup.2+b.sup.2).sup.1/2

[0285] As can be seen from Table 18, it can be seen that Example 9 had a color-strengthening effect according to repeated use.

(5) Sensory Evaluation

[0286] Meanwhile, a sensory evaluation was performed to evaluate the smoothness of the treated hair. The results are shown in Table 19 below. The experiment was conducted on 15 male and 15 female subjects, and they were required to evaluate the conditioning effect of the hair based on the evaluation criteria of smoothness. Experiment #16 is the results of treating the hair with the anionic surfactant sodium lauryl sulfate without treatment of a polymer. Experiment #17 is the results of sensory evaluation of hair which was washed once with the shampoo prepared using the polymer of Example 9, and Experiment #18 is the results thereof using the polymer of Comparative Example 23.

[0287] Evaluation CriteriaThe order of hair freshness was measured, and the opposite represents roughness.

[0288] (5: Very good); (4: Good); (3: Moderate); (2: Bad); (1: Very bad)

TABLE-US-00019 TABLE 19 Experiment Experiment Experiment Experimental Category #16 #17 #18 Sensory Evaluation 1.5 4.5 4.5

[0289] As shown in Table 19, it can be seen that excellent effect was actually exhibited even in terms of the conditioning effect. This is because the molecular weight of the polymer was much larger than the molecular weight of the hair dye components bound to the glucose ring, and thus the hair dye component did not interfere with the surface smoothness after adsorption to hair, which can be confirmed from the fact that there was no difference between Experiments #17 and #18.

4. Properties of Transferring Active Ingredient of Cationic Polymer to which the Active Ingredient are Bound to Hair, Skin, or Fiber

[0290] (1) Preparation of Cationic Polymers Bound with Hair Dyes

[0291] Cationic cellulose polymers were prepared according to the above-mentioned 1. One of the reactive blue No. 4 dye and 5-([4,6-dichlorotriazin-2-yl]amino) fluorescein was selected and allowed to bind to the carbon at position 2 of the glucose monomer as shown in Reaction Schemes 1 and 2 below. The dyes can be used as a phosphor and a hair dye, and thus can grasp the polymer adsorption position of the active ingredient and utilize the dye function at the same time. The cellulose polymer bound with the reactive blue No. 4 is represented by Chemical Formula 3, and the cellulose polymer bound with 5-([4,6-dichlorotriazin-2-yl]amino) fluorescein is represented by Chemical Formula 4. The polymer of Chemical Formula 3 has a fluorescence emission color and a visible light reflection color of blue, and the polymer of Formula 4 has a fluorescence emission color of green while having a visible light reflection color of orange.

##STR00006##

[0292] In Chemical Formula 3, x is an integer of 1 to 10, and when y is 1, n is 0.3 to 0.7.

##STR00007##

[0293] In Chemical Formula 4, x is an integer of 1 to 10, and when y is 1, n is 0.3 to 0.7.

[0294] The cellulose polymer prepared as described above was adjusted of its pH using KOH, and then stirred at 500 rpm, filtered with HPLC-grade ethanol, and subjected to freeze-drying (Bondiro, IlshinBio) for one week. When aggregation occurs due to the binding between the amine group and the carboxyl group of 5-([4,6-dichlorotriazin-2-yl]amino) fluorescein in the cellulose polymer represented by Chemical Formula 4, the aggregate can be decomposed by stirring with a homo mixer, if necessary.

(2) Change in Adsorption Layer Thickness According to Molecular Weight

[0295] In order to evaluate the adsorption characteristics of cationic polymers to the substrate, the method practiced in the art including Dow Corning, a raw-material manufacturing company for conditioning agents, was used. More specifically, mica, which has a Zeta potential of tens of mV, similar to those of hair and wool, was selected as the substrate, and the cationic polymers were adsorbed onto the mica substrate to determine the adsorption characteristics of the polymers.

[0296] 12 mm diameter mica discs (TED PELLA, Canada) were used as an adsorbent. The polymers were placed and adsorbed onto only half of the mica discs using 10 ml of distilled water containing 0.5% of polymers, and then washed with distilled water. The adsorption of cationic cellulose polymers is determined by the electrostatic action between the mica and the polymer adsorbed onto the mica. Since the content of the polymer in an aqueous solution does not affect the amount of adsorption, 0.5% aqueous solution, which is a mixing amount conventionally used in the compositions for hair, was selected and used.

[0297] The interface between the adsorbed polymer layer and the mica bottom was observed by the atomic force microscopy (AFM, Model Systems XE-100, Korea) using the topography of the contact mode of the tip, and the result is shown in FIG. 1.

[0298] The molecular weight of the polymers used to evaluate the adsorption layer characteristics in the 0.5% aqueous solution is shown in Table 20 below.

TABLE-US-00020 TABLE 20 Comparative Comparative Comparative Example Example Example Example Example Example Samples 25 26 27 11 12 13 Molecular 600,000 1,000,000 1,200,000 1,500,000 2,100,000 3,000,000 Weight

[0299] The change in the thickness of the adsorption layer according to the molecular weight of polymers was measured according to the number of adsorptions and is shown in Table 21 and FIG. 8. (Unit: m).

TABLE-US-00021 TABLE 21 Comparative Comparative Comparative Number of Example Example Example Example Example Example adsorptions 25 26 27 11 12 13 0 0 0 0 0 0 0 1 0.52 0.68 0.69 0.78 0.47 0.50 3 0.37 0.40 0.42 0.54 0.78 0.38 5 0.35 0.37 0.39 0.12 0.16 0.54 7 0.38 0.38 0.40 0.18 0.18 0.47 9 0.37 0.42 0.41 0.42 0.52 0.65 11 0.38 0.37 0.40 0.38 0.47 0.49 13 0.37 0.38 0.41 0.14 0.15 0.69 15 0.40 0.39 0.39 0.30 0.18 0.52 17 0.39 0.41 0.40 0.55 0.47 0.73

[0300] As can be seen from the results of Table 21 and FIG. 8, it was confirmed that Comparative Examples 25 to 27 showed a constant adsorption thickness despite repeated number of adsorptions, whereas Examples 11 to 13 showed that the thickness of the adsorption layer fluctuated within a particular range. These results confirmed that the cellulose polymers according to the present invention having a molecular weight within a particular range exhibited a phenomenon of adsorption layer fluctuation.

[0301] More specifically, Comparative Examples 25 to 27 showed the highest adsorption thickness for one-time adsorption, and it can be understood therefrom that the cationic cellulose polymers were constantly adsorbed onto the space on the negatively charged surface. However, starting from the third-time adsorption, the thickness of the adsorption layer started to decrease, and it can be understood therefrom that the adsorption force was lowered due to the cationic repulsive force with the adsorption layer already formed, and thus the additional adsorption layer was washed down during the rinsing process, in the case in which the anionic surface was fully covered with the cationic cellulose polymer and then the cationic cellulose polymer was further adsorbed onto a single layer having an overall negative charge

(3) Analysis of Adsorption Layer Components Using Confocal Fluorescence Microscopy

[0302] In order to confirm the phenomenon of the adsorption layer fluctuation estimated by the fluctuation of the adsorption layer thickness in (2) above, the following experiment was performed.

[0303] First, an experiment was performed on the cellulose polymers to which a fluorescent dye was bound using a confocal fluorescence microscope (LSM710, Carl Zeiss). The cellulose polymers of Comparative Example 25 and Example 11 were used. First, the polymer bound with a blue fluorescent dye was adsorbed onto mica discs and washed three times, and then the polymer bound with a green fluorescent dye was continuously adsorbed onto mica discs and washed three times.

[0304] Then, the thus-treated mica discs were irradiated with a laser light having a wavelength of 420 nm and 510 nm, and the fluorescence spectrum was mapped onto the bottom with an area of 100 m100 m. Thereafter, the most top and most bottom parts of the treated mica discs were focused and mapped, and the results are shown in FIG. 3.

[0305] As can be confirmed from FIG. 9, in the case of the polymer (A) of Comparative Example 25, only the blue fluorescent polymer was detected at both the bottom and top parts of the mica discs, and no green fluorescence was detected. Through these results, it was confirmed that after the polymer of Comparative Example 25 was adsorbed onto the mica discs, the cellulose polymer bound with the green fluorescent dye was not further adsorbed onto the mica discs.

[0306] In contrast, in the case of the polymer (B) of Example 11, both blue fluorescence and green fluorescence were detected at both the bottom and top parts of the mica discs. Accordingly, it was confirmed that the polymer bound with the blue fluorescence and the polymer bound with the green fluorescence formed an adsorption layer due to the fluctuation of the adsorption layer of the polymer of Example 11. From these results, it can be seen that the previously adsorbed cationic polymer was substituted with the cationic cellulose of the present invention having a molecular weight of 1,500,000 or more thus being capable of transferring the active ingredients.

(4) Confirmation of Phenomenon of Adsorption Layer Fluctuation Through Hair Dyeing

[0307] In order to confirm the effect of the cellulose polymer according to the present invention when it was applied to hair, which is an actual biological substrate, the following experiment was conducted.

[0308] The polymers used in the experiment were polymers having the molecular weights of Comparative Example 25 and Example and 11. The result obtained from the use of Comparative Example 15 was denoted by (A) and the result obtained from the use of Example 11 was denoted by (B).

[0309] First, a 0.5% aqueous solution of the cellulose polymer bound with a blue dye was applied in an amount of 1 ml per 1 g of yak hair, and after 30 seconds, the yak hair was washed with running water for 30 seconds and the water thereon was removed using a dryer. The hair at this time was denoted as 1) in each of A and B in FIG. 10.

[0310] Then, the cellulose polymer bound with an orange dye was additionally applied under the same conditions as in Example 11 of (2) above, and after 30 seconds, the hair was washed with running water for 30 seconds and the water thereon was removed using a dryer. The hair at this time was denoted as 2) in each of A and B in FIG. 10.

[0311] Finally, the cellulose polymer bound with the blue dye was applied, and after 30 seconds, the hair was washed with running water for 30 seconds and the water thereon was removed using a dryer. The hair at this time was denoted as 3) in each of A and B of FIG. 10.

[0312] As can be seen from FIG. 10, it was confirmed that, in the case of Comparative Example 25, no additional adsorption layer was formed when an additional polymer was applied according to the adsorption of 1) to 3). In contrast, in the case of Example 11, a violet dye, which is an interference color between a blue dye and an orange dye, was observed, and accordingly, it was confirmed that the color of hair dye was changed through the adsorption layer fluctuation of the polymer. This result reflects that the orange dye layer adsorbed for the second time and the blue dye layer adsorbed for the third time were mixed rather than being accumulated in order.

[0313] Through this experiment, it was confirmed that the active ingredients can be continuously transferred through the fluctuation of the cellulose polymer adsorption layer in the actual biological materials.

(5) Evaluation of Continuous Conditioning Effect

[0314] The conditioning effect was evaluated by applying cellulose polymers, to which hair oil was bound, to the hair.

[0315] The cellulose polymers of Comparative Example 25 and Example 11 were used in the experiment, and C.sub.15 to C.sub.20 alkyl groups were added using a halohydrin at the position in each glucose monomer to prepare cellulose polymers bound with oil.

[0316] The prepared polymers were used to prepare a shampoo composition with the composition shown in Table 22 below. The preparation of the shampoo composition was carried out according to a conventional method. After the cellulose polymers were dissolved in purified water, a surfactant was added in sequence and dissolved, and then the pH was adjusted by adding EDTA 4Na and citric acid monohydrate. As other ingredients, preservatives, fragrances, dispersants, viscosity modifiers, and pH modifiers were added.

TABLE-US-00022 TABLE 22 Shampoo Shampoo Preparation Preparation Ingredients (wt %) Example 1 Example 2 Jojoba oil 0.1 0.1 Polymer (Example of using the 0.5 polymer of Comparative Example 25) Polymer (Example of using the 0.5 polymer of Example 11) Sodium laureth sulfate 8 8 Cocamidopropyl betaine 4.5 4.5 EDTA 4Na, citric acid monohydrate 0.1 0.1 Other ingredients 16 16 Purified water Residual amount Residual amount (to 100) (to 100)

[0317] 1 g hair tress was treated with shampoo for 50 seconds using each of the above Shampoo Preparation Example 1 and Shampoo Preparation Example 2 prepared with the above composition and then rinsed with running water at a flow rate of 4 ml/sec for 2 minutes, and this whole process was repeated 60 times. After heating the hair for 60 minutes at 65 C. using an evaporator (Mettler Toledo, US), the change in hair mass of 0.5 g was measured to evaluate the change in moisture content of the hair. The results are shown in Table 23 below.

TABLE-US-00023 TABLE 23 Shampoo Preparation Shampoo Preparation Example 1 Example 2 Mass Change % 19.2 23.2

[0318] As confirmed in Table 23, the change in hair mass was large when the Shampoo Preparation Example 2 was used. This indicates that the amount of moisture contained in the hair was relatively increased. That is, it was confirmed that the oil transferred by the cellulose polymer was continuously transferred to the hair surface cuticle due to the fluctuation phenomenon inside the adsorption layer, and the moisture release from the hair was prevented, thereby providing a moisturizing effect to the hair.

[0319] Additionally, sensory evaluation was conducted on 15 men and 15 women with respect to the hair treated with the Shampoo Preparation Examples 1 and 2 and the control as described above for softness. As the control, hair, which was treated with a 10% aqueous solution of sodium lauryl sulfate as an anionic surfactant in the same manner as above, was used without treatment of any polymer.

Evaluation Criteria

[0320] 5Very good (soft), 4Good, 3Moderate, 2Bad, 1Very bad (rough)

TABLE-US-00024 TABLE 24 Use of Shampoo Use of Shampoo Preparation Example Preparation Example 1 2 Use of Control Sensory 3.2 4.6 1.7 Evaluation

[0321] As can be seen in Table 24, the conditioning effect was observed when the Shampoo Preparation Examples 1 and 2 were used, and it was confirmed that the effect was remarkably excellent in the case of using the Shampoo Preparation Example 2 containing the polymer that exhibits the adsorption layer fluctuation.

5. Property of Preventing Loss of Hair, Skin, or Fiber Components of Cationic Polymers

(1) Preparation of Cationic Polymers

[0322] Cationic cellulose polymers were prepared according to the above-mentioned 1. Specifically, a cationic cellulose polymer having a molecular weight of 800,000 and a nitrogen content (% by weight) of 2.7%, wherein is EO and is OH in the Chemical Formula 1; a cationic cellulose polymer having a molecular weight of 800,000 and a nitrogen content (% by weight) of 2.7%, wherein is EO (divalent or higher) and is OH; a cationic cellulose polymer having a molecular weight of 800,000 and a nitrogen content (% by weight) of 2.7%, wherein is EO (divalent or higher) and is EO (monovalent or higher); a cationic cellulose polymer having a molecular weight of 1,800,000 and a nitrogen content (% by weight) of 2.7%, wherein is EO (divalent or higher) and is OH; and a cationic cellulose polymer having a molecular weight of 2,500,000 and a nitrogen content (% by weight) of 2.7%, wherein is EO (divalent or higher) and is OH were synthesized and used in the following tests. In addition, under the same conditions as above, a cationic cellulose polymer having a nitrogen content of 1.7% by weight was also synthesized and used in subsequent experiments.

(2) Preparation of Washing Solution Composition

[0323] The shampoo washing solution composition was prepared in a conventional manner according to the prescription shown in Table 25 below. The composition was prepared by varying the amount of the polymer and/or oil included in the washing solution according to the following Examples or Comparative Examples. Specifically, after adding the polymer, surfactants were added in sequence and dissolved, and the pH was neutralized by adding EDTA.4Na and citric acid monohydrate. As other ingredients, preservatives, fragrances, dispersants, viscosity modifiers, and pH modifiers were added.

TABLE-US-00025 TABLE 25 Mixing Ingredients Weight (%) Polymer and/or oil 1.0 Sodium lauryl sulfate (SLS) 8 Cocamidopropyl betaine 4.5 EDTA 4Na, citric acid monohydrate 0.1 Other ingredients 16 Purified water Residual amount (to 100)

[0324] Next, a conditioner was prepared as shown in Table 26.

TABLE-US-00026 TABLE 26 Mixing Ingredients Weight (%) Purified water 75 Glyceryl stearate 0.1 Cetearyl alcohol 5 Behentrimonium chloride 2 Purified water Residual amount (to 100)

(3) Lipid Quantification Through GC/MS Spectrum

1) Evaluation Method

[0325] For the shampoo treatment, 1 g of hair tress was treated with 1 ml of shampoo, lathered for 45 seconds by rubbing, and rinsed with water for 2 minutes at a flow rate of 4 ml/sec, and this whole process was repeated 5 times. Next, the hair was allowed to stand at 50% RH condition in a constant temperature and humidity chamber for one day and then finely crushed with intervals of 1 mm. Lipids were extracted with a solvent mixture of chloroform and methanol using an ultrasonic washing machine (Branson, 3510E) for 4 days and analyzed by gas chromatography GC/MS (Agilent 5977B GC/MSD) in a SIM mode.

[0326] For GC/MS analysis, marker materials were prepared by mixing with a solution prepared by mixing chloroform and methanol in a ratio of 2:1 and at 5000 ppm. As the internal solution, tricosanoic acid was used at 50 ppm. Ionization voltage was 70 eV at 250 C., and HP-5 ms UI column (30 m0.25 mm0.25 m) was used. The temperature was raised from 80 C. to 320 C. by 5 C. per minute. In all experiments, the population was n=10.

2) Evaluation According to Polymer Type

Experiments #9 to #22

[0327] The hair was treated 10 times with the shampoo composition of Table 25, which includes LR30M as a polymer, and the quantitative value obtained by GC/MS analysis was calculated as a relative value based on the GC/MS quantitative value of un-shampooed hair, which was set to 100%, and the analysis results are shown in Table 27. The group A includes myristyl acid (C.sub.14), palmitic acid (C.sub.16), stearic acid (C.sub.18), oleic acid (C.sub.18=1), and cholesterol, and the group B includes lipids having strong hydrophobicity, such as squalene, wax esters of C.sub.14-C.sub.14, C.sub.14-C.sub.16, C.sub.16-C.sub.16, C.sub.18-C.sub.16. The results in Table 27 mean the content of each lipid, indicating the relative value (%) based on the control group (GC/MS quantitative value of un-shampooed hair).

TABLE-US-00027 TABLE 27 Content for short-term Content for long-term treatment (%) treatment (%) Experiment Experiment Experiment Experiment Type of Lipids #19 #20 #21 #22 Lipid C.sub.14 75 1 68 2 65 3 59 1 Group C.sub.16 72 1 66 1 63 2 57 1 A C.sub.18 70 1 68 1 63 2 59 1 C.sub.18 = 1 75 1 73 1 62 3 59 1 Cholesterol 76 1 74 1 73 2 72 1 Lipid Squalene 57 2 82 1 43 1 75 1 Group C.sub.14-C.sub.16 61 2 76 9 45 3 45 3 B C.sub.16-C.sub.16 55 1 58 6 42 2 36 1 C.sub.18-C.sub.16 55 1 71 1 48 6 46 6 C.sub.14-C.sub.14 57 3 77 6 48 4 67 5

[0328] Specifically, for Experiment #19, a 10% diluted shampoo solution in the composition of Table 25 was used, and the hair was washed 10 times by hand under constant physical pressure. The washing was performed by lathering for 50 seconds with the shampoo solution and washing for 2 minutes. Since the hair was brought into contact with the actual shampoo solution for 10 minutes, Experiment #20 was carried out by stirring in a shaker (Jeio Tech, SI-900R, Korea) for 10 minutes under the same concentration conditions. Experiment #20 was different from Experiment #19 in that the washing was performed without physical pressure.

[0329] Experiment #21 was performed for 30 minutes using the treatment of Experiment #19, and Experiment #22 was performed under the same conditions as Experiment #20 by increasing the treatment time by 30 minutes.

[0330] As a result, as shown in Table 27 and FIG. 12, it was observed that the lipid loss patterns of Experiments #19 and #21, in which infiltration of the surfactants were induced by applying physical pressure in the short-term and long-term treatments, were different from the lipid loss patterns of Experiments #20 and #22, which were performed without physical pressure.

[0331] It was confirmed that, in Experiments #19 and #21, lipids of group B with hydrophobicity were lost in larger amounts as compared to those in group A with relatively low hydrophobicity or amphipathicity, whereas in Experiments #20 and #22, the lipids of the group A with amphipathicity or relatively low hydrophobicity (particularly lower than the lipids of group B) were lost in larger amounts than the lipids of group B.

[0332] Although Experiments #19 and #21 have the same concentration of shampoo solution as Experiments #20 and #22, aggregation occurred by coacervation in Experiments #19 and #21, so that the hair was brought into contact with the shampoo solution at a high concentration, that is, the anionic surfactant at a high concentration. Additionally, since friction and physical pressure were applied to the hair by hand, the surfactants could more easily infiltrate into the hair, and the infiltrated surfactants could easily bind to the hydrophobic components inside the hair. Regarding the infiltration of the molecules into the hair, it has been reported previously that when the ratio of the amphoteric surfactant to the anionic surfactant is 2:1, spherical micelles are formed instead of cylindrical micelles (Langmuir, 20, (2004) 571) at 150 mM or below, and it is not known whether hair micelles infiltrate directly into the hair, or whether surfactant monomolecules infiltrate into the hair and re-form micelles, but it was proved that the surfactants infiltrate into the hair by imaging the surfactant micelles with CryoTEM (transmission electron microscopy) at a size of 6.00.6 nm (Langmuir, 4 (1988) 1066). For reference, the largest size of micelle observed was 4.8 nm (Langmuir, 4 (1988) 1066) and the presence of micelles in the outer part of the hair was confirmed using energy-dispersive X-ray spectroscopy (EDX) via imaging (Int. J. Cos. Sci. 26 (2004) 61). Therefore, according to the results of the above conventional studies, if it were assumed that the anionic surfactant infiltrated into the hair during the washing process and formed micelles, it was predicted that lipids of the group B having hydrophobicity would be captured by the micelles which infiltrated inside of the hair, and would be lost by exiting the hair.

[0333] As shown in Experiments #20 and #22, the lipids of the group A slowly exited at a relatively low concentration over time and were lost in large amounts. In the washing process, since the lipids of the group A in the hair are not completely hydrophobic, there is a high probability that not all of the lipids would be captured in the micelles formed by the surfactant. Therefore, the lipids of the group A are not lost by the surfactant in the inside, but are eluted to the outside by the phenomenon in which the lipids inside the hair escape to the outside, that is, by the diffusion of the lipids (J. Cosmet. Sci., 49, (1998) 223). It was confirmed that the lipids of the group A migrated towards the outside of the hair by diffusion and exited and then were lost when the lipids were brought into contact with the anionic surfactant present outside the hair.

(4) Hair Surface Treatment

[0334] It was confirmed that the lipids of the group A were lost in the outer layer of the hair by the anionic surfactants. Therefore, in order to reduce the probability of the contact of the anionic surfactant with the lipids by suppressing the diffusion of the lipids of the group A, the shampoo composition of Table 25 and the conditioner compositions of Table 26 were prepared according to the prescription shown in Table 28 and applied on the hair. The conditioner was also applied once at a time after shampooing, and the washing was repeated 10 times in total. After each washing cycle, the hair was completely dried with a dryer to promote diffusion by heat.

[0335] Various sebum and grease residues remain on the hair, and the hair washed once with sodium laurate sulfate (SLES) was set as Comparative Preparation Example 1. As reported in the previous studies, in the case of light washing, lipids at a depth of 3 nm of hair remained (J, Cosmet Sci. 61 (6) (2010), 467-77), and thus, the washing of Comparative Preparation Example 1 was carried out on the assumption that the internal lipids were not eluted.

[0336] In Comparative Preparation Example 2, a Ucare LK cationic cellulose polymer PQ10 having a nitrogen content of 0.5% by weight was used as the polymer in the mixing of Table 25, and in Comparative Preparation Example 3, an LR30M cationic cellulose polymer PQ10 having a nitrogen content of 1.0% by weight was used as the polymer in the mixing of Table 1.

[0337] In Comparative Preparation Examples 4 and 5, Abil WAX 9840 and WAX9801 manufactured by Evonik were used, which had an interfacial tension of 120 mN/m or higher in the mixing of Table 25, respectively.

[0338] In Preparation Examples 3 and 4, cationic cellulose polymers (: EO (bivalent or higher), : OH, and molecular weight of 800,000) having a nitrogen content of 1.7% and 2.8% by weight, respectively, were synthesized and used as the polymer in the mixing of Table 25. In Preparation Examples 5 and 6, were treated with shampoo, which selectively included TEGOSOFT APM and TEGOSOFT E having an interfacial tension between water/oil of 100 mN/m or less, respectively, and was stirred.

TABLE-US-00028 TABLE 28 Comparative Comparative Comparative Comparative Comparative Preparation Preparation Preparation Preparation Preparation Preparation Preparation Preparation Preparation Example Example Example Example Example Example Example Example Example Samples 1 2 3 3 4 4 5 5 6 N content 0.5 1.0 1.7 2.8 1.0 1.0 1.0 1.0 in polymer (wt %) Polar oil 160 120 100 90 (mM/m)

TABLE-US-00029 TABLE 29 Comparative Comparative Comparative Comparative Comparative Preparation Preparation Preparation Preparation Preparation Preparation Preparation Preparation Preparation Example Example Example Example Example Example Example Example Example Lipids 1 2 3 3 4 4 5 5 6 Total 100% 36% 36% 52% 54% 36% 37% 47% 48% content of Group A Total 100% 38% 38% 39% 40% 37% 37% 37% 37% content of Group B

[0339] Table 29 shows the average content of the lipids of the group A and the lipids of the group B (amount remained in hair after washing) as a percentage relative to the control value (Comparative Preparation Example 1). According to the results of Preparation Examples 3 and 4 of Table 29, it can be seen that when the shampoo treatment was carried out using high-cationic polymers, the loss of the lipids of the group A could be prevented, while the lipids of the group B could not be protected. In Preparation Examples 5 and 6, similarly, it can be seen that the lipids of the group A were better protected when oils having an interfacial tension of 100 mN/m or less were used. When comparing Preparation Examples 3 and 4 with Preparation Examples 5 and 6, a more excellent effect of preventing lipid loss was exhibited when the polymer was included rather than the polar oil. This is because the anionic surfactants were bound to other oils and polymers instead of the lipids diffused out of the hair. Even when the cationic cellulose polymers were adsorbed onto the surface of the hair and bound to the surfactants, it would be difficult for the polymers to be eluted out due to the properties of polymers, and accordingly, the film layer would not be lost in the hair. Additionally, the polar oil or the polymers having a high nitrogen content increased the charge density on the surface of the hair, which lowered the interfacial tension on the surface of the hair, thereby reducing the contact angle of the lipids, and consequently, the lipids of the group A, which had weak hydrophobicity, was prevented from being lost by surfactants that came into contact with them when exposed to the surface.

(5) Protection of Lipids of Group B: Internal Treatment of Hair

[0340] As a crosslinking-mediating component, polylysine, polyamine, or soy protein was used for forming an amine bond with hair, and polycarbodiimide (PCI) was used for crosslinking them together (Table 30). According to the prescription of Table 25, a composition including a crosslinking-mediating component and polycarbodiimide of Table 30 below was added to a shampoo composition prepared by including a PQ10 polymer (LR30M) having a nitrogen content of 1.0% as a polymer, and the resultant was stirred at room temperature for 10 minutes at 400 rpm. Then, the lipid content in the hair was measured in the same manner as in (4) above.

[0341] Each lipid content of the hair, treated with the shampoo to which the crosslinking-mediating component and PCI of Table 30 were added, was calculated as a relative value (%) based on the lipid content value in the hair washed once with sodium laurate sulfate (SLES) of Comparative Preparation Example 1, and the results are shown in Table 31. For easy comparison of the behavioral properties according to the lipids, the average content of the five lipid components including myristyl acid, palmitic acid, stearic acid, oleic acid, and cholesterol is shown by the content of the group A lipids, and the average content of the four lipid components including squalene, wax esters of C.sub.14-C.sub.14, C.sub.14-C.sub.16, C.sub.16-C.sub.16, C.sub.18-C.sub.16, is shown by the content of the group B lipids.

TABLE-US-00030 TABLE 30 Preparation Preparation Preparation Samples Example 7 Example 8 Example 9 Polylysine 0.5% Polyamine 0.5% Soy protein (WS-SP) 0.5% PCI 0.5% 0.5% 0.5%

TABLE-US-00031 TABLE 31 Preparation Preparation Preparation Lipid Content Example 7 Example 8 Example 9 Lipids of Group A 36% 36% 37% Lipids of Group B 42% 47% 46%

[0342] As shown in Table 31, it was confirmed that the crosslinking was effective in protecting the lipids of the group B. However, the crosslinking had no protective effect on the loss of the group A lipids. That is, it was confirmed that when the inside of the hair was densely filled with crosslinking, the elution of the hydrophobic lipids of the group B by infiltration of surfactant micelles into the hair and capturing the lipids could be prevented, while the elution of the relatively less hydrophobic lipids of the group A by diffusion into the outside could not be prevented. Accordingly, the following experiment was conducted to provide a composition capable of preventing the loss of both the hydrophobic components and the amphipathic/low hydrophobic components.

(6) Simultaneous Protection of Lipids of Groups A and B

[0343] In Tables 29 and 31, it was confirmed that the loss of lipids of the groups A and B was prevented, and in order to confirm the protective effect for all of the lipids, shampoos and conditioner compositions of Tables 25 and 26 were prepared according to the prescription of Table 32. Table 33 shows the values of GC/MS quantitative analysis by washing the hair tress 10 times in the same manner as in (4) described above. In Preparation Example 11, a cationic cellulose polymer having a nitrogen content of 1.7% by weight (: EO (bivalent or higher) and : OH, molecular weight of 800,000) was synthesized and used, and in Preparation Example 13, a cationic cellulose polymer having a nitrogen content of 2.8% by weight (: EO (bivalent or higher) and : OH, molecular weight of 800,000) was synthesized and used. In Preparation Examples 10 and 12 to 13, TEGOSOFT APM (PPG-3 myristyl ether) manufactured by TEGOSOFT having an interfacial tension of 100 mM/m was used as oil. The lipid contents shown Table 33 were averaged as a relative value (%) based on the control value of Comparative Production Example 1. The content of each component in Table 32 means the content of the component relative to the total composition as a weight percent.

TABLE-US-00032 TABLE 32 Preparation Preparation Preparation Preparation Samples Example 10 Example 11 Example 12 Example 13 Polymer 0.5 0.5 0.34 Oil 0.5 0.5 0.33 Polylysine & PCI 0.5 0.5 0.33

TABLE-US-00033 TABLE 33 Preparation Preparation Preparation Preparation Lipid Content Example 10 Example 11 Example 12 Example 13 Lipids of Group B 79% 76% 68% 99% Lipids of Group A 46% 67% 64% 99%

[0344] It can be seen that the prescription containing a high cationic polymer and a polar oil maintained the lipid content of the group A very efficiently (Preparation Example 10), but the loss of lipids of the group B was only slightly protected. The effect of preventing the lipid loss was only slightly increased in the group B than in Preparation Examples 3 to 6 of Table 29, these results appear to be because the frictional force was reduced during the washing process, thereby reducing the damage of cuticle layer, and at the same time, the oil content decreased the infiltration of the surfactant micelles, resulting in a decrease in the loss of the lipids in the group B.

[0345] In Preparation Examples 11 to 12 of Table 33, the effect of protecting both the loss of lipids of the groups A and B was exhibited. Particularly, in Preparation Example 13, a surprising effect of protecting most of the lipids was exhibited. The reason for the occurrence of a synergistic effect in the protection be interpreted that the outer monomolecular oil or polymer cationic coating film reduces the number of micelles infiltrating into the inside as well as to the outside, and simultaneously, that when the polar oil infiltrates into the inside as well as to the surface, it interferes with the flow of the lipids diffused therein together with the tightly bound crosslinks, ultimately almost completely protecting the lipids during the washing process.

(7) Evaluation of Physical Properties by Treatment with Composition of Preparation Example 13

1) Evaluation of Bending Strength of Hair

[0346] In order to confirm the effect of protecting the loss of lipids on the hair, and in order to evaluate the strength of the hairs treated with each of the compositions of Comparative Preparation Examples 1 (experimental group in which no elution of the internal lipids occurred) and 2, or Preparation Example 11, Preparation Example 12, and Preparation Example 13, the bending strength was evaluated using KES-FB2-S(KATO TECH, Japan), a bending strength tester. The strength of the hair was increased as the bending strength increased.

[0347] A sample tress was prepared in which 200 hairs of shampoo-treated hair having a thickness of 70 to 80 m were attached into a 10 cm size without gaps. This evaluation method was carried out according to the manual recommended by KATO TECH, and when evaluating the bending strength of fiber tress, measurement was performed according to the evaluation method adopted as a standard evaluation by the public institution for fiber evaluation.

Results of Bending Strength Evaluation

[0348] The results evaluated with the fiber strength tester are shown in Table 34 below.

TABLE-US-00034 TABLE 34 Pre- Pre- Pre- Comparative Comparative paration paration paration Preparation Preparation Example Example Example Samples Example 1 Example 2 11 12 13 Bending 0.576 0.466 0.513 0.489 0.573 Strength (Unit: gf cm)

[0349] As shown in Table 34, the bending strength was significantly lowered after 10 washings as in Comparative Production Example 2, that is, it was found that the strength of the hair was significantly reduced when the hair was washed 10 times. However, in Preparation Example 13, the strength of hair was almost at the same level as compared to that before washing.

2) Sensory Evaluation of Hair

[0350] Based on the above results, shampoos were prepared and sensory evaluation was carried out. The experiment was conducted on 15 male and 15 female subjects, and they were required to evaluate the hair-strengthening effect after shampooing based on the following evaluation criteria of smoothness.

[0351] The strength was determined by the following criteria in the order of hair strength (the opposite was stiff): (5: Very flexible); (4: Flexible); (3: Moderate); (2: Stiff); (1: Very stiff)

[0352] The trimness and calmness were evaluated by the following evaluation criteria according to the degree of trimness seen from the upper head (the opposite was puffy): (5: Very calm); (4: Calm); (3: Moderate); (2: Puffy); (1: Very puffy)

[0353] L80KC, a guar gum polymer generally prescribed for commercially available hair-strengthening shampoos, was prescribed as a polymer of Table 1 to prepare a composition, which was treated in Experiments #23 and #24, and in Experiment #25 with the prescription of Preparation Example 13.

[0354] The results are shown in Table 35 below as average values.

TABLE-US-00035 TABLE 35 Experimental Experiment Experiment Experiment Category #23 #24 #25 Strongness 3.6 3.8 4.6 Calmness 2.4 2.5 4.8

[0355] As can be seen from Experiment #25 in Table 35, it can be seen that the shampoo of the present invention significantly increased the strength compared to the conventional hair-strengthening shampoos. Additionally, the effect of hair trimness and calmness was also observed, and in Experiment #25, an effect of observing no baby hair was exhibited as it tended to stick to the hair regardless of whether it was curly, half-curly, or straight hair. Accordingly, it can be seen therefrom that the active ingredients were efficiently transferred to various forms of human hair by the adsorption according to the composition of the present invention.

3) Evaluation of Surface Friction of Hair

[0356] Subsequently, for the shampoos having the polymer composition of the present invention, the frictional force was quantified through device evaluation in order to evaluate the conditioning effect for imparting softness and feeling of use.

Experimental Method

[0357] Comparative Preparation Examples 1 and 2, a hair-strengthening shampoo of LG Household & Health Care, and the composition of Preparation Example 13 were added to a burex hair tress at 10% by weight based on the weight of hair, and the hair was lathered for 15 seconds, rubbed for 20 seconds, and rinsed for 15 seconds with running water at 37 C., and then wiped with a towel to remove moisture. Thereafter, the friction was evaluated using an MTT 175 Miniature Tensile Tester (DiaSTRONG, GB).

[0358] The shampoo-treated hair was rinsed for 2 minutes and then dried with a dryer for 2 minutes. The hair was kept at 25 C. in a constant temperature and humidity chamber under a humidity of 50% for one day, so that the moisture in the hair was kept constant, and then the frictional force was measured in the same temperature and humidity chamber. Here, the percentage (%) divided by the frictional force value (reference value), after washing the hair tress with the anionic surfactant sodium lauryl sulfate, was calculated and is shown in Table 12 below. In this case, the hair was smoother as the frictional force (%) increased.

Results

[0359]

TABLE-US-00036 TABLE 36 Experiment Experiment Experiment #26 #27 #28 Experiment (Comparative (Comparative (Hair- #29 Experimental Preparation Preparation strengthening (Preparation Category Example 1) Example 2) shampoo) Example 13) During 4% 55% 37% 56% rinsing After drying 6% 21% 26% 29%

[0360] From the results shown in Table 36 above, the shampoo having the polymer composition of the present invention remarkably reduced frictional force, thereby increasing the conditioning effect for imparting smoothness. In particular, in the case of the commercial hair-strengthening shampoo, the smoothing effect was reduced as shown in Experiment #28. In other words, as can be seen from the above embodiments, it was confirmed that the polymer composition prepared by the present invention exhibited the effect of strengthening the bending strength (weakening the flexibility) by preventing the loss of lipids when applied to a conditioning agent, and at the same time, the polymer composition of the present invention was found to be a component for excellent hair conditioning cosmetic compositions for imparting smoothness.

(4) Tensile Strength

[0361] Four hair tresses (12 cm in length, 3 g in weight) made of damaged hair by bleaching twice were prepared. The tensile strength (unit: cN, 1 gf=0.98 cN) of 100 strands of hair was measured in each hair tress, and the average value was calculated and set as a reference value. In this case, a tensile strength measuring device manufactured by DIASTRON was used to measure the tensile strength.

[0362] Subsequently, each hair tress was immersed in each of the compositions according to Experiments #26 to #29 of Table 36, except for Experiment #29, for 10 minutes and then washed for 30 seconds with running water. Thereafter, the hair was dried at room temperature (about 25 C.) for 24 hours. The tensile strength (cN) of the 100 strands of hair was measured in each hair tress treated as described above, and the average value was calculated. The results are shown in Table 37 below.

TABLE-US-00037 TABLE 37 Experiment Experiment Experiment #26 #27 #28 Experiment (Comparative (Comparative (Hair- #29 Experimental Preparation Preparation strengthening (Preparation Category Example 1) Example 2) shampoo) Example 13) Before 142 cN 139 cN 141 cN 142 cN treatment After 141 cN 112 cN 123 cN 165 cN treatment Enhancement 1 27 18 +23

[0363] As shown in Table 37, it can be seen that the tensile strength was decreased in all other treatment groups, but the tensile strength of the hair was increased only in Preparation Example 13 (Experiment #29) even after washing with shampoo. Therefore, it can be seen that the composition of the present invention also has an effect of increasing the tensile strength of the hair by preventing the loss of internal components of the hair.

5) Evaluation of Glossiness

[0364] Four hair tresses (12 cm in length, 3 g in weight) made of damaged hair by bleaching twice were prepared, and glossiness was measured using SAMBA (Bossa Nova Tech., USA). The glossiness was evaluated by first measuring the front and back of the tress to adjust the glossiness to a value of 8.5, and then treating the hair with the compositions of Preparation Examples and Comparative Preparation Examples in the same manner and under the same condition as the method of measuring the rate of change of the tensile strength.

TABLE-US-00038 TABLE 38 Experiment Experiment Experiment #26 #27 #28 Experiment (Comparative (Comparative (Hair- #29 Experimental Preparation Preparation strengthening (Preparation Category Example 1) Example 2) shampoo) Example 13) Before 8.5 8.5 8.5 8.5 treatment After 8.0 7.0 9.0 19.5 treatment Enhancement -0.5 -1.5 +0.5 +11

[0365] As shown in Table 38, it can be seen that all other treatment groups showed a decrease in glossiness, but the glossiness was significantly increased only in Preparation Example 13. Thus, it can be seen therefrom that the composition of the present invention not only protects the lipids during the washing process, and at the same time, exhibits the effect of significantly increasing the glossiness to the hair by providing calmness and trimness to the hair.

[0366] From the above description, it will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. In this regard, it should be understood that the above-described embodiments are to be considered in all respects as illustrative and not restrictive. Furthermore, the scope of the present invention is defined by the appended claims rather than the detailed description, and it should be understood that all modifications or variations derived from the meanings and scope of the present invention and equivalents thereof are included in the scope of the appended claims.