KR102139350B1 - Dye-Enhancement Functional Polymer for Shampoo and Detergent Composition Comprising the Same - Google Patents

Abstract

The present invention discloses a polymer in which a reactive dye is covalently bound to cationic cellulose. When the polymer is used as a detergent composition together with an anionic surfactant, coacervate is formed upon dilution in water, so that the hair dyeing effect may not be inhibited by the anionic surfactant, and the hair dyeing effect is enhanced through cumulative adsorption upon repeated use of the cleaning agent composition. Can be.

Description

Dye-Enhancement Functional Polymer for Shampoo and Detergent Composition Comprising the Same}

The present invention relates to a dye-strengthening functional polymer for shampoos and a detergent composition comprising the same.

Hair cosmetics generally have the function of removing hair and scalp, and keeping the hair clean and beautiful. In addition, the hair cosmetic product is used for additional purposes such as changing and supplying hair color in addition to the above functions, ease of combing, softening, smoothing or glossing the hair, reducing friction on the surface of the hair, preventing static electricity, or protecting the hair.

Hair dyes change the hair color by penetrating the dyeing component into the cortex by adjusting the pH to open and close the cuticle. However, since this has the effect of damaging the health of the hair and scalp, temporary hair dyes have been used in recent years.

The temporary hair dye adsorbs a color-tinging component on the outer cuticle layer of the hair, but because the temporary hair dye molecule has cationic properties, it can adsorb to anionic hair, but it is based on anionic surfactants in hair cosmetics. Since the hair dye effect is inhibited or the dyeing function is lost due to the combination with a cleaning agent such as a shampoo to be used, it is difficult to apply to a shampoo, and thus there is a limit to use only a treatment agent.

On the other hand, there is a document that discloses a dye composition using a polymer in which a polymer and a hair dye are combined (WO 2011-113680 A2), but this only discloses a polymer such as polyamine, and does not recognize cationic cellulose as a polymer. , There is no suggestion as to the applicability to shampoos containing anionic surfactants.

Against this background, the present inventors first prepared a polymer in which a reactive dye was combined with a cationic cellulose polymer. Particularly, when it is used as a detergent composition with anionic surfactant, it is confirmed that coacervate is formed upon dilution in water, so that the hair dye effect may not be inhibited by the anionic surfactant, and the hair dye effect can be enhanced through cumulative adsorption when repeatedly used. Thus, the present invention was completed.

One object of the present invention is to provide a dye-enhancing functional polymer for shampoo.

Another object of the present invention is to provide a detergent composition containing the polymer and anionic surfactant.

Another object of the present invention is to provide a method for dyeing hair, comprising the step of washing the hair using the composition.

Hereinafter, the present invention will be described in more detail.

Meanwhile, each description and embodiment disclosed herein may be applied to each other description and embodiment. That is, all combinations of the various elements disclosed herein are within the scope of the present invention. In addition, it cannot be said that the scope of the present invention is limited by the specific description described below.

In addition, one of ordinary skill in the art can recognize or identify a number of equivalents to certain aspects of the invention described in this application using only routine experimentation. In addition, such equivalents are intended to be included in the present invention.

As one aspect of the present invention for solving the above problems, the present invention provides a polymer having the following formula (1).

[Formula 1]

이나 모두 H는 아니며,Where n Q are each independently H or

But not all H,

R ₁ , R ₂ , and R ₃ are each independently C _1-6 alkyl, alkenyl, or alkynyl, m is an integer from 1 to 10, γ is H or OH;

x is an integer from 1 to 100;

n is an integer from 10 to 1000;

α and β are each independently O(CH ₂ CH ₂ O) _s H where s is an integer from 0 to 100;

The active ingredient delivered to the active ingredient delivered to the anionic substrate is bound to at least one terminal of the α and β.

The polymer of the present invention has a function of efficiently delivering an active ingredient to OH attached to carbon 2 and/or 3 of cationic cellulose or anionic substrate attached to a polyethylene glycol linker terminal bound thereto. For example, if a reactive dye is used as an active ingredient, the reactive dye can be transferred to hair or the like, and thus can be used for dyeing or strengthening.

In addition, by using quaternary ammonium bound to the 6th carbon of cationic cellulose, coacervate is formed when diluted in water using with an anionic surfactant, so that the hair dyeing effect is not inhibited by the anionic surfactant and at the same time strengthening the dyeing function. It can be used as a cleaning agent having a.

인 Q의 개수의 비율은 1:0.2 내지 1:0.8, 구체적으로, 1:0.3 내지 1:0.7 보다 구체적으로 1:0.4 내지 1:0.6 일 수 있다. 상기 범위를 갖는 폴리머는 음이온성 계면활성제와 함께 물에 희석시 코아세르베이트를 안정적으로 형성할 수 있다. Q의 개수 비율이 0.8보다 많을 경우 양이온화도가 높아져 점도가 상승하여 코아세르베이트를 형성할 폴리머 결합량이 작아지고 샴푸 제형을 만들기 어려운 문제가 있으며, 0.2 보다 적을 경우 양이온화도가 낮아져 음이온계면활성제와의 결합력이 낮아 세정과정에서 코아세르베이트의 기능 저하 문제가 생길 수 있다. In Formula 1 n:

The ratio of the number of phosphorus Q may be 1:0.2 to 1:0.8, specifically 1:0.3 to 1:0.7, and more specifically 1:0.4 to 1:0.6. The polymer having the above range can stably form coacervate when diluted in water with anionic surfactant. When the number ratio of Q is greater than 0.8, the degree of cationicity increases, the viscosity increases, and the amount of polymer bonds to form coacervate becomes small, making it difficult to make a shampoo formulation, and if it is less than 0.2, the degree of cationicity decreases and the binding force with anionic surfactants decreases. It may be low, which may cause the problem of deterioration of coacervate in the cleaning process.

In particular, when the polymer has a viscosity of 20 cps to 500 cps, specifically 50 cps to 500 cps, in the composition containing 1 to 3% by weight, hair color is increased by repeated use. When the viscosity is higher than 500 cps, the adsorption layer is not increased by repeated use, and when the viscosity is lower than 20 cps, adsorption becomes difficult to appear.

Viscosity of the composition is a value that increases as the molecular weight of the polymer increases, excellent adsorption and desorption capacity when the molecular weight of the polymer has a value of 10,000 to 400,000, specifically 50,000 to 350,000, and more specifically 100,000 to 300,000. Indicates. Specifically, when the molecular weight of the cationic cellulose polymer exceeds 400,000, if additional adsorption occurs, there is a property that additional adsorption is prevented by mutual electric repulsive force between the cationic polymer layer adsorbed on the substrate and the cationic polymer to be adsorbed. In the rinsing process, the polymer adsorption layer having a high molecular weight has hydrophilicity over a large area, so it is easily dissolved in water and rather desorbed. In particular, when the molecular weight of the polymer is high, there are many adsorption trains (adsorption part) and loops (non-adsorption part) in the state adsorbed on the anionic substrate, and thus entropy is large, so that it is easily detached from contact with water molecules. When the molecular weight is less than 10,000, the adsorbed area is small, making it difficult to detect the color change and the smoothing effect of conditioning.

As used herein, the term "anionic substrate" means a substrate that exhibits anionic properties such as hair, skin, and fibers. The anionic substrate can be adsorbed by the electrostatic attraction and the polymer layer of the present invention showing cationic properties, so that the active ingredient bound to the polymer can be easily transferred.

The active ingredient may be a reactive dye.

As used herein, the term "reactive dye" refers to a dye that is chemically reacted with a functional group such as hair, skin, or fiber, and is dyeed by covalent or ionic bonding. Reactive dyes are known to have excellent fastness properties because the reactive group has covalent bonds with hair, skin, or fibers.

The reactive dye as described above is not limited to the type as long as it is known in the art. The detailed description is known from Industrial Dyes (K.Hunger edition, Wiley VCH 2003) and the like, and commonly used reactive dyes are color indexes [Society of Dyers and Colourists] and American Textile Chemical Technology Dyeing Technology Association (American Association of Textile Chemists and Colorists).

Specifically, covalent reactive dyes include dichlorotriazinyl, difluorochloro pyrimidine, monofluorotriazinyl, dichloroquinoxaline, vinyl sulfone, difluorotriazine, monochlorotriazinyl, bromoacrylamide and trichloro And a reactor selected from pyrimidines. More specifically, the reaction dye includes a reactor selected from monochlorotriazinyl, dichlorotriazinyl and vinylsulfonyl.

In addition, the reactive dye preferably includes a chromophore selected from azo, anthraquinone, phthalocyanine, formazan and tripendioxazine.

The reactive dye may contain 0 to 4 SO ₃ Na groups, thereby allowing an effective level of negative charge to be generated.

Examples of reactive dyes include reactive blue 4 dye, reactive black 5 dye, reactive blue 19 dye, reactive red 2 dye, reactive blue 59 dye, reactive blue 269 dye, reactive blue 11 dye, reactive yellow No. 17 dye, Reactive Orange No. 4 dye, Reactive Orange No. 16 dye, Reactive Green No. 19 dye, Reactive Brown No. 2 dye, Reactive Brown No. 50 dye, and the like are not limited thereto.

As the ion-binding reactive dye, a basic raw material notified in the Ministry of Food and Drug Safety Notification No. 2016-49 can be selected. Basic raw materials can be adsorbed by cation or cation part of zwitterion by ion bonding to anionic hair, basic brown 16, basic blue 99, basic red 76, basic brown 17, basic yellow 87 Arc, basic yellow 57, basic red 51, basic orange 31, and the like, but is not limited thereto. There are other acid raw materials, which have anionic charge, but can be adsorbed by sticking to the hydrophobic part of the hair and stick to the cationic adsorbent polymer adsorbed on the hair, but are not limited to, such as acidic red No. 52, acidic red 92, etc. .

In the present embodiment, a reactive blue 4 dye and 5-([4,6-dichlorotriazin-2-yl), which are used as phosphors and can simultaneously utilize the dye function, are used to determine the position of polymer adsorption. ]Amino) fluorosein was used as a reactive dye, but is not limited to a reactive dye used as a phosphor.

As another aspect of the present invention for solving the above problems, the present invention provides a detergent composition containing the polymer and anionic surfactant.

Specifically, the detergent composition may be treated on an anionic site such as hair or skin. The detergent composition may be applied to fibers such as hair to exhibit a dyeing function or to enhance the dyed color.

Specifically, when the cleaning agent composition is treated on undyed hair, it may be dyed. In addition, it is possible to enhance the color already dyed by washing the hair with the cleaning agent composition on the hair dyed by another dyeing method. In this case, a detergent composition comprising a polymer bound with a dye having the same or similar color as the dyed hair can be used.

As anionic surfactant, sodium lauryl sulfate, sodium laureth sulfate, polyoxyethylene sodium lauryl sulfate, ammonium lauryl sulfosuccinate, ammonium myresulfate, disodium laureth sulfosuccinate, disodium C12-C14 pareth-2 Sulfosuccinate, or mixtures thereof, and the like can be used. The anionic surfactant may be included in 1 to 30% by weight, specifically 3 to 20% by weight based on the total weight of the composition. The amphoteric surfactant may be included in an amount of 0.1 to 20% by weight, specifically 2 to 15% by weight, based on the total weight of the composition.

The detergent composition of the present invention may further include a nonionic surfactant and/or amphoteric surfactant. Examples of nonionic surfactants include lauryl acid diethanolamide, palm oil fatty acid diethanolamide and palm oil fatty acid monoethanolamide, and examples of amphoteric surfactants include betaines, cocamidopropyl betaine, and alkylglycinate. And alkylaminopropionate, but is not limited thereto. The nonionic surfactant and amphoteric surfactant may be included in an amount of 0 to 15% by weight, specifically 1 to 15% by weight, and more specifically 3 to 10% by weight based on the total weight of the composition.

The cleaning composition of the present invention may include an oil used for moisturizing or moisturizing the hair. Any oil that can change the moisture content in the hair by adsorbing and penetrating the hair can be used without limitation.

Non-limiting examples of the oil include components commonly referred to as silicones such as water-insoluble, non-volatile dimethicone, cyclomethicone, aminated silicone, trimethylsilyl adimethicone or vinyl silicone, and derivatives thereof, and vegetable products such as jojoba oil. Oils, vegetable oils, animal oils, animal oils, hydrocarbon oils or synthetic ester oils and the like can be used. Hydrocarbon oil may be liquid paraffin, isoparaffin, or hydrogenated polydecene, and ester oil may include isopropyl myristate, isopropyl palmitate, isostearyl isostearate, or C12-15 alkyl benzoate, triethylhexanoin, and squalane. , Palm oil, Olea Europaea oil, PPG-3 caprylyl ether, capric/caprylic triglyceride, isostearyl isostearate Isostearate, Coconut (Cocos Nucifera), Polyglyceryl-6 octacaprylate, Hydrogenated polydecene, Jojoba Seed Oil, DI-C 12-13 alkyl marrate, etc. may be used, but is not limited thereto. Jojoba oil was used as the oil in this example.

The oil may be included in 0.05 to 4% by weight, specifically 0.1 to 2% by weight.

The detergent composition of the present invention can be used as a shampoo.

In this case, in order to enhance the conditioning effect, it may further include additional adjuvants used in the art without detracting from the object of the present invention. For example, fats, organic solvents, solubilizers, thickeners, gelling agents, emollients, antioxidants, suspending agents, stabilizers, blowing agents, fragrances, surfactants, water, ionic or non-additives commonly used in hair compositions are additionally used. It may include any one or more selected from the group containing ionic emulsifiers, fillers, metal ion blockers, preservatives, vitamins, blockers, wetting agents, essential oils, dyes, pigments, hydrophilic or lipophilic actives.

In addition, the composition of the present invention may further include additives that provide beneficial properties to the human body. For example, washing, volume, trimming, protection, blocking, moisturizing, dyeing, coloring, bleaching, restriction, deodorization, antiseptic, refreshing, hair removal, hair growth, dandruff prevention, hair loss prevention, wool, anti-inflammatory, incense, aroma, whitening, Anti-aging, wrinkle improvement, convergence, relaxation, contraction, sebum suppression, exfoliation, sterilization, anti-inflammatory, Jinyang, deodorization, antihistamine, anti-seborrhea, blood circulation promotion, sun protection or skin metabolism promotion Additives may be further included.

In addition to this, the composition of the present invention may further contain preservatives, thickeners, viscosity modifiers, pH modifiers, flavoring agents, dyes or conditioning agents, etc., which can be commonly used as components of a composition for hair, and these are commercially easily purchased. Can be used. Examples of preservatives include benzoic acid and salts, methyl paraoxybenzoate, methylchloroisothiazolinone or a mixture of methylisothiazolinone (trade name: Kathon CG, manufacturer: The Dow Chemical Company). As a thickener and a viscosity modifier, hydroxypropylmethylcellulose, hydroxymethylcellulose, sodium chloride, ammonium chloride, propylene glycol, hexylene glycol, sodium xylene sulfone, or ammonium xylene sulfonate may be used. Citric acid, sodium hydroxide or triethanolamine may be used as the pH adjusting agent. As the dye, water-soluble tar color or the like may be used. In addition, as a conditioning agent, animal and vegetable extracts, protein and protein variants, and Fatty Acid may be used.

The composition of the present invention can be prepared in the form of a general emulsifying formulation or a solubilizing formulation.

In addition, the composition of the present invention can be prepared in any formulation that can be applied to the scalp, such as liquid, cream, paste or solid.

In addition, the composition of the present invention may be any one formulation selected from the group comprising shampoo, hair conditioner, hair lotion, hair essence, hair gel, hair pack, patch and spray.

As another aspect of the present invention for solving the above problems, the present invention provides a method for dyeing hair, comprising washing the hair using the cleaning agent composition.

Specifically, the hair may be repeatedly washed 1 to 10 times using the cleaning agent composition. Through repeated washing, the degree of hair coloring on the hair can be enhanced.

Methods of dyeing hair include dyeing undyed hair and enhancing color on already dyed hair.

It shows the hair dye effect of the hair through a reactive dye bound to the cationic cellulose polymer of the present invention. When this is used as a detergent composition together with an anionic surfactant, coacervate is formed upon dilution in water, so that the hair dye effect may not be inhibited by the anionic surfactant, and the hair dye effect can be enhanced through cumulative adsorption when the detergent composition is repeatedly used. .

1 is a graph showing the thickness of a polymer film adsorbed on mica by AFM according to the number of adsorption. FIG. 1(A) shows Example 2 and FIG. 1(B) shows the thickness change of Comparative Example 2.
2 is a confocal fluorescence microscope image. 1(A) shows Example 2 and FIG. 1(B) shows the bottom and top images of the adsorption layer of Comparative Example 2.
Figure 3 is a photograph of applying a dye to the hair, Figure 3 (A) shows Example 2, Figure 3 (B) shows Comparative Example 2.

Hereinafter, examples and the like will be described in detail to help understanding of the present invention. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be interpreted as being limited to the following examples. The embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Manufacturing example One: Cationic With polymer Combination of active ingredients

In the following examples and comparative examples, raw materials synthesized by the present inventors were used. In the polymerization process, the molecular weight was adjusted by changing the content of ethyl cellulose, and the nitrogen content was adjusted by changing the amount of trimethylamine to control the content of the degree of cationization.

A quaternized ammonium salt was prepared by quaternization reaction with hydroxy ethyl cellulose and chlorohydroxypropyl trimethylamine.

Specifically, sodium hydroxide and urea were mixed in a solvent of water at a concentration ratio of 7.5:11:81.5 (sodium hydroxide:urea:water), and then hydroxy ethyl cellulose was dissolved at a concentration of 2% by weight. Subsequently, the quaternary ammonium-based compound is further contained at an appropriate excess concentration (3, 6, 9 times the number of moles compared to the glucose ring of cellulose), and the reaction proceeds according to the conditions of temperature (25, 45, 60°C) to modify the chemical formula. A quaternary cationic cellulose polymer of 1 was prepared.

In addition, EO (ethylene oxide) addition or alkylation was performed with reference to the reference (WO 2016085099 A1) to prepare a structure containing an alkyl group.

Specifically, gas phase polymerization using epoxide was performed to add ethylene oxide (EO) to α and β positions in the glucose ring of the cationic cellulose polymer, and the temperature and pressure were injected after the reactants were injected in the chamber. The reaction was carried out to add EO.

Reactive blue 4 dye and 5-([4,6-dichlorotriazin-2-yl) that can simultaneously utilize the dye function that can be used as a phosphor and hair dye effect to determine the location of polymer adsorption as an active ingredient ]amino)fluorescein was selected and bound to position 2 of the glucose monomer carbon as shown in Reaction Schemes 1 and 2. The former has a fluorescence emission color and a visible light reflection blue color, and the latter has a green fluorescence emission color, but has a bright red orange color under visible light.

[Scheme 1]

[Scheme 2]

First, the pH was lowered to KOH, the dye was stirred at 500 rpm with the polymer, and then filtered with HPLC grade ethanol, followed by freeze-drying for a week (Bondiro, Ilshin). However, as shown in Chemical Formula 3, aggregation occurs between the amine group of the polymer and the carboxyl group of 5-([4,6-dichlorotriazin-2-yl]amino)fluorescein. It can be decomposed by stirring the mixer.

Experimental Example 1: according to viscosity and molecular weight Adsorption layer Thickness change

In order to evaluate the adsorption state of the cationic polymer bound with reactive blue No. 4, the method used by many companies, such as the raw material for conditioning agents, Dow coning, and the amount of anionic charge of several tens of mV, which is generally similar to that of hair and skin, is used. A mica having (Zeta potential) was selected as a substrate, and a cationic polymer was adsorbed on the mica substrate to determine the adsorption properties of the polymer.

A 12 mm diameter mica disk (TED PELLA, Canada) was used as an adsorption object. Using 10 ml of distilled water containing 0.5% of polymer, the polymer was adsorbed by standing on only half of the mica disk, and then washed with distilled water. The amount of polymer adsorption is determined by the electrical attraction and repulsive force between the polymer and the polymer adsorbed on the mica. In addition, since the desorption proceeds due to the hydrophilicity of the polymer and water, the change in the amount of the polymer is not a factor affecting the amount of adsorption, so 0.5%, which is the amount of the polymer normally used in shampoo, was selected as the experimental condition.

The boundary between the adsorbed polymer layer and the bottom of the mica is thickened by contact mode topography of Cantilever (NSC36C, MikroMasch, Germany) using atomic force microscopy (hereinafter AFM, Model XE-100, Korea, Park Systems). The evaluation results are shown in FIG. 1.

Examples 1 to 3 and Comparative Examples 1 to 3 having the viscosity of Table 1 were prepared for thickness variation experiments according to polymer viscosity and molecular weight.

sample Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Viscosity (2%) 50 200 500 600 700 800 Molecular Weight 100,000 200,000 300,000 500,000 700,000 900,000

Table 2 shows the thickness change of the adsorption layer according to the polymer molecular weight.

Adsorption frequency Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 0 0 0 0 0 0 0 One 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: μm)

Looking at the results shown in Table 2 and Figure 1, in Examples 1 to 3 of the polymer having a viscosity of 50 to 500 in the aqueous solution state and a molecular weight of 100,000 to 300,000, the thickness adsorbed according to the additional adsorption It can be seen that is increasing.

In Comparative Examples 1 to 3, the adsorption thickness of the adsorption layer is constant as the number of adsorption increases, and it seems that the adsorption layer does not undergo further adsorption by rinsing power in the bonding relationship between the adsorption layer and the cationic polymer.

Experimental Example 2: Confocal Using a fluorescence microscope Adsorption layer Ingredient analysis

After discovering that the polymer adsorption pattern is divided into three types in the results of Table 2, experiments were conducted with a confocal fluorescence microscope as in Experimental Example 2 to confirm why this variation occurred.

The cellulose polymer to which the fluorescent dye was bound was tested with a confocal fluorescence microscope (Carl Zeiss, LSM710). By selecting the polymers of Example 2 and Comparative Example 2, first, the polymer bound with the reactive blue No. 4 dye was adsorbed and washed three times on the mica disk, and then the green fluorescent dye (5-([4,6-dichlorotriazin) The -2-yl]amino)fluorescein)-bound polymer was continuously adsorbed and washed on a mica disk. Excitation light wavelengths of 420nm and 510nm are scanned for laser light to map the fluorescence spectrum to the bottom with a 100μmX100μm area, and then the topmost and bottommost parts are focused and mapped, as shown in FIG. 2.

As shown in FIG. 2(A), the polymer of Example 2 had a blue bottom, but no green was detected. However, the blue fluorescent polymer was not detected in the uppermost part, while only the green part was detected. That is, when the green binding polymer is accumulated and adsorbed on the blue binding polymer, it indicates that the accumulated adsorption continues on the conventional adsorption layer every time the polymer is adsorbed.

The polymer of Comparative Example 2 is shown in FIG. 2(B), but only the blue fluorescent polymer was detected below and above, and the green fluorescent polymer was not detected. This means that after the adsorption of the blue polymer proceeds, no further adsorption proceeds.

Experimental Example 3: Cumulative phenomenon applied to hair

It was confirmed as shown in FIG. 3 that a change occurs after adsorption of a polymer by applying it with an anionic surfactant-based shampoo to hair, which is an actual biological substrate.

According to the prescription shown in Table 3, a shampoo composition was prepared by a conventional method.

Ingredients Weight ratio (%) Jojoba oil 0.1 Polymer 0.5 Sodium laureth sulfate 8 Cocamidopropyl Betaine 4.5 EDTA 4Na, hydrous citric acid 0.1 Other ingredients 16 Purified water Remaining amount (to 100)

Since the cellulose-based polymer has excellent solubility, after the polymer is added, a surfactant is added and dissolved several times, and then EDTA·4Na and hydrous citric acid are added to neutralize the pH. Other ingredients were added preservatives, fragrances, dispersants, viscosity modifiers and pH modifiers.

The 1g hair tress was treated with the shampoo for 50 seconds and rinsed for 2 minutes at a flow rate of 4 ml/second. 1), 2), and 3) in FIG. 3 are cleaned after a single treatment, two repeated treatments, and three repeated treatments, respectively.

The polymer of Example 2 in which adsorption proceeds according to the number of adsorption, the hair color was enhanced according to the dye color as the number of treatments increased as shown in FIG. 3(A). On the other hand, as in Comparative Example 2, the polymer for preventing further adsorption was constant in blue as the first dyeing color, regardless of the additional dyeing, as shown in FIG. 3(B).

Through the above examples, it was found that dyeing is actually enhanced when applied to hair.

Table 4 shows shampoos prepared by attaching a reactive blue No. 4 dye to a polymer having a viscosity of 200 cps used in Example 2 and a polymer containing a reactive blue No. 4 dye to a polymer having a viscosity of 700 cps used in Comparative Example 2 as in Table 3. And the result of color change is expressed as CIE lab value through a color difference meter.

sample Example 1 Comparative Example 1 blue green yellow blue green yellow One 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

Colorimeter reading, ΔE=(L ² +a ² +b ² ) ^1/2

As can be seen from Table 4, it can be seen that Example 1 has a color enhancing effect according to repeated use.

Experimental Example 4: sensory evaluation

Meanwhile, sensory evaluation was performed to evaluate the smoothness of the treated hair, and the results are shown in Table 5 below. The experiment was conducted on 15 men and women, and the conditioning effect of the hair was evaluated based on the following evaluation criteria for smoothness. Experiment #1 is the result of treatment with anionic surfactant sodium lauryl sulfate without treatment of the polymer, experiment #2 is the polymer of Example 2, experiment #3 is the shampoo using the polymer of Comparative Example 2 once washed hair Sensory evaluation value.

Evaluation Criteria-Measurement of the order in which hair smoothness is felt, and the opposite is rough

(5: very good); (4: excellent); (3: normal); (2: bad); (1: very bad)

Experimental classification Experiment #1 Experiment #2 Experiment #3 Sensory evaluation 1.5 4.5 4.5

It can be seen that, as shown in Table 5, it shows excellent efficacy in terms of conditioning. This can be seen from the fact that there is no difference between experiments #2 and #3 that the hair dye component does not interfere with the surface smoothness after hair absorption because the polymer molecular weight is much larger than the molecular weight of the hair dye component bound to the glucose ring.

From the above description, those skilled in the art to which the present invention pertains will appreciate that the present invention may be implemented in other specific forms without changing its technical spirit or essential characteristics. In this regard, the embodiments described above should be understood as illustrative in all respects and not restrictive. The scope of the present invention should be construed as including the meaning and scope of the claims, which will be described later, rather than the above detailed description, and all modified or modified forms derived from the equivalent concepts thereof.

Claims (13)

Polymer having Formula 1
[Formula 1]

Where n Q are each independently H or

But not all H,
R ₁ , R ₂ , and R ₃ are each independently C _1-6 alkyl, alkenyl, or alkynyl, m is an integer from 1 to 10, γ is H or OH;
x is an integer from 1 to 100;
n is an integer from 10 to 1000;
α and β are each independently O(CH ₂ CH ₂ O) _s H where s is an integer from 0 to 100;
A reactive dye delivered to the anionic substrate is bound to at least one of the α and β ends. The polymer according to claim 1, wherein the polymer has a molecular weight of 10,000 to 400,000. The polymer of claim 1, wherein the anionic substrate is hair or skin. delete The method of claim 1, wherein n:

The ratio of the number of phosphorus Q is 1:0.2 to 1:0.8, the polymer. The polymer of claim 1, wherein the polymer has a viscosity of 20 to 500 cps in an aqueous solution of 1 to 3% by weight. The method of claim 1, wherein the reactive dye is dichlorotriazinyl, difluorochloro pyrimidine, monofluoro triazinyl, dichloroquinoxaline, vinyl sulfone, difluorotriazine, monochloro triazinyl, bromo acrylamide and triclo. A polymer comprising a reactor selected from lopyrimidine. The polymer of claim 1, wherein the reactive dye comprises a chromophore selected from azo, anthraquinone, phthalocyanine, formazan, and tripendioxazine. The polymer of claim 1, wherein the reactive dye is reactive blue 4 dye or 5-([4,6-dichlorotriazin-2-yl]amino)fluorosein. A detergent composition comprising the polymer of any one of claims 1 to 3 and 5 to 9 and an anionic surfactant. The method of claim 10,
The polymer is to be included from 0.01 to 1% by weight based on the total weight of the composition, composition. The method of claim 10,
The anionic surfactant is 2 to 30% by weight based on the total weight of the composition, the composition. A method of dyeing hair, comprising washing the hair using the composition of claim 10.

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