KR102263749B1 - Conditioning polymer inhibits build-up of adsorption film upon, and composition comprising the same - Google Patents

Abstract

The present invention relates to a cationic cellulose polymer having a nitrogen content of 2.3 to 3.2% by weight based on the total weight of the polymer and a molecular weight of 30 to 2.9 million, and a composition for hair treatment or fiber treatment comprising the same. The composition for hair or fiber treatment comprising the polymer of the present invention improves freshness by preventing the cumulative adsorption of hair, and significantly increases smoothness, thereby having excellent hair conditioning effect.

Description

Conditioning polymer inhibits build-up of adsorption film upon, and composition comprising the same

The present invention relates to a cationic cellulose polymer for preventing cumulative adsorption and a composition comprising the same, and more particularly, to a cationic cellulose polymer capable of preventing cumulative adsorption by optimizing molecular weight and nitrogen content.

Hair cosmetics generally have a function for washing hair by removing contamination of the scalp and hair, and keeping the hair clean and beautiful. In addition to the above functions, hair cosmetics are also used for additional purposes such as ease of combing, imparting softness, smoothness or shine to hair, reducing friction on the hair surface, preventing static electricity, or protecting hair.

In order to impart a conditioning effect to the hair, the hair cosmetic composition generally includes a cationic polymer, a cationic surfactant, silicone or oil, and the like. Repeated use of these chemical components may cause hair, pore or scalp troubles due to cumulative adsorption, which is due to skin allergies and inflammation that reacted with chemical components. In particular, when the cumulative adsorption of the cationic polymer among the ingredients used is excessive, the hair cosmetic composition has a disadvantage of drying the hair, as well as a decrease in elasticity, a decrease in the degree of smoothness, and a problem in that the hair becomes stiff. In the case of fabric softeners used for the purpose of fabric flexibility, cationic polymers, cationic surfactants, silicones or oils are used. As with hair cosmetics, if the cationic polymer accumulates a lot, the fibers become stiff, contrary to the purpose of use. In particular, when the cationic polymer of the shampoo used for a smooth conditioning feeling is adsorbed to the hair having an anion and has a cumulative adsorption layer, a polymer feeling is generated and the hair becomes stiff. Avoid the use of highly cationic polymers in targeted shampoos.

Cationic cellulose is adsorbed to anionic hair when shampooing to give it a conditioning function, but when repeated use, cumulative adsorption occurs and the above problems occur. Attempts are being made to develop effective polymers. According to common sense, when cationic cellulose is used, when the nitrogen content in the cationic cellulose is reduced, the degree of cationization is lowered, and it is thought that the cumulative adsorption phenomenon to the hair or fiber with an anion can be improved, so that the nitrogen content is usually 1.8 wt% or less. Materials with nitrogen content exist and are commonly used. In addition, the production of cellulose with a high nitrogen content is difficult due to the limited yield according to the repeated manufacturing process and the increase in the steric hindrance of cellulose by the cationization reaction to make the nitrogen content of 1.8% by weight or more. There are no related material products. situation is not.

As a result, there was no attempt to improve the cumulative adsorption phenomenon of the polymer by adjusting the actual nitrogen content, and furthermore, there was no attempt to reduce the cumulative adsorption phenomenon by increasing the cationization degree of the polymer. This is because what often happens is an expected result from common sense and scientific background.

Republic of Korea Patent Publication No. 2008-0019017

An object of the present invention is to provide a polymer that reduces the cumulative adsorption phenomenon by increasing the degree of cationization and controlling the molecular weight.

An object of the present invention is to provide a cationic polymer as a conditioning agent for hair or fibers that can remove the stiff feel of hair or fibers caused by cumulative adsorption even after repeated use and improve the conditioning effect of hair or fibers.

The present invention is to provide the cationic polymer as a composition for preventing the accumulation of adsorption. In addition, the present invention is to provide a composition for hair or fiber treatment comprising the cationic polymer.

A first aspect of the present invention provides a cationic cellulose polymer having a nitrogen content of 2.3 to 3.2% by weight and a molecular weight of 300,000 to 2.9 million based on the total weight of the polymer.

A second aspect of the present invention provides a composition for preventing accumulation of adsorption comprising the cationic cellulose polymer of the first aspect of the present invention.

A third aspect of the present invention provides a composition for treating hair or fibers comprising the cationic cellulose polymer of the first aspect of the present invention.

Hereinafter, the present invention will be described in detail.

The present inventors have made intensive research efforts to overcome the problem that cationic cellulose, which adsorbs to hair or fibers and imparts a conditioning function, is adsorbed to hair or fibers when repeatedly used, resulting in a cumulative adsorption layer and stiffening of hair or fibers. As a result, cationic cellulose In the hair conditioning agent composition containing the cellulose polymer, the molecular weight of the cationic cellulose polymer is 300,000 to 2.9 million and the nitrogen content is adjusted to 2.3 to 3.2% by weight based on the total weight of the polymer. When the degree of cationization is secured, the accumulation of hair or fibers It has been found that adsorption is prevented and that it has a conditioning effect on the hair or fibers. Accordingly, the present invention found that, when the composition containing the cationic cellulose polymer is used for hair or fiber treatment, the cumulative adsorption phenomenon of hair or fibers is prevented, and the hair becomes soft and the fiber has a fiber softening effect. The present invention is based on this.

The present invention provides a cationic cellulose polymer capable of preventing cumulative adsorption during hair or fiber treatment.

The cationic cellulose polymer serves to impart conditioning effects such as gloss and softness to hair or fibers.

The present invention is characterized by the development of an optimal molecular weight and nitrogen content range of a cationic polymer that can prevent cumulative adsorption and impart a conditioning effect to hair or fibers even during repeated use.

In the cationic cellulose polymer of the present invention, ethylene oxide (EO) or OH bonded to the 2nd and 3rd carbons of the glucose unit in the cellulose backbone can be hydrogen-bonded, and the OH site bonded to the 6th carbon is a linker. It may be a cationic cellulose polymer into which a cationic quaternary ammonium that is not capable of hydrogen bonding is introduced. The cationic polymer may be a cationic cellulose polymer having a nitrogen content of 2.3 to 3.2% by weight based on the total weight of the polymer, and a molecular weight of 300,000 to 2.9 million.

The cationic cellulose polymer of the present invention may be a quaternized ammonium salt comprising hydroxy ethyl cellulose and trimethylamine.

Alternatively, the preparation reaction of the cationic cellulose polymer of the present invention (this preparation method is referred to as reaction 1) is to prepare a quaternary ammonium salt obtained by quaternizing hydroxyethyl cellulose with chlorohydroxypropyl trimethylamine. can

Specifically, sodium hydroxide and urea are contained in a concentration of 7 to 9: 10 to 12: 75 to 85 (sodium hydroxide: urea: water) with respect to water as a solvent, and then hydroxyethyl cellulose is added to 1 to 3 wt. It can be prepared by dissolving it at a concentration of %, and then adding a quaternary ammonium-based compound. More specifically, after sodium hydroxide and urea are contained at a concentration of 7.5:11:81.5 (sodium hydroxide:urea:water) with respect to water as a solvent, hydroxyethyl cellulose is dissolved at a concentration of 2 wt%. can The solvent of the above composition helps to improve the solubility and stability of hydroxyethyl cellulose, thereby helping to improve the uniformity of the modification in the reaction process. [Bi Xiong, Dissolution of cellulose in aqueous NaOH/urea solution: role of urea, Cellulose (2014) 21: 1183-1192] After that, the quaternary ammonium-based compound was added to an appropriate concentration (1 mole or more moles relative to the glucose unit of cellulose). ), and the reaction proceeds according to room temperature or heating conditions to be modified.

There are three positions in the glucose ring having a hydroxyl group that can be modified: C2, C3, and C6. Among them, C6 primary alcohols generally have excellent regioselectivity for reforming reactions because they have minimal steric hindrance. On the other hand, the difference in the reforming reaction preference between C2 and C3 is claimed differently depending on the conditions such as the solvent system. [Mitsuru Abe, Regioselectivity in Acetylation of Cellulose in Ionic Liquids, Materials Science inc. Nanomaterials & Polymers (2016) 1: 2474-2478]

The cationic cellulose polymer of the present invention may be a polymer substituted with ethylene oxide (EO) at the α and β positions in the glucose ring. In addition, as a comparative example, the height of the film according to repeated adsorption was evaluated using a polymer substituted with an alkyl group at the α-position in the glucose ring as a cellulose polymer. Reference "Cation-modified cellulosic fabric and its manufacturing method (WO 2016085099 A1)" and proceeding with ethylene oxide (ethylene oxide; EO) addition or alkylation (alkylation) to prepare a structure containing an alkyl group have.

In the case of adding EO to the α and β positions in the glucose ring, gas phase polymerization using epoxide is carried out, the reactants in the chamber are sprayed, and then the heating and pressurization reaction is performed to proceed with the EO addition. In the case of alkylation, the reaction may proceed so that a desired alkyl group may be added using a reactant having a terminal functional group of halohydrin, aldehyde, or epoxide.

In an embodiment of the present invention, EO was added to the α or β position in glucose of a cationic cellulose polymer substituted with trimethylamine, and as a comparative example, alkylation was repeated at the α position in glucose to attach a functional group. . As a result, when EO is added to the α or β position in glucose, when the polymer is repeatedly used, the adsorption power is lowered due to the cationic repulsion force with the polymer already adsorbed to the hair or fiber surface, and at the same time, the polymer adsorbed to the hair is α and β Because hydrogen bonds can be formed at the position, they are washed away by hydrophilicity with water, and finally, the effect of preventing the accumulation of cationic polymers from adsorption was shown. On the other hand, in the case of the alkylated cationic cellulose polymer, it was confirmed that the affinity with water molecules decreased due to the increase in hydrophobicity due to alkyl, and the phenomenon of rinsing the polymer with water was reduced.

Therefore, specifically, the cationic cellulose polymer of the present invention may be one in which EO is added to the α or β position in the glucose ring.

In addition, in order to increase the nitrogen content of the quaternary ammonium salt in the cationic polymer of the present invention, the amount of trimethylamine is changed and the addition reaction process of the quaternary ammonium compound of Reaction 1 described above is repeated while controlling the temperature condition. As a result, by adjusting the nitrogen content, it is possible to control the content of the degree of cationization. This was confirmed through elemental content analysis.

The cationic cellulose polymer may be a quaternary ammonium salt represented by Formula 1 below.

In the above formula, x may be 1 to 10, preferably 1 to 5, more preferably 1 to 3. In the above formula, when n is 1, y may be 0.3 to 0.7, preferably 0.4 to 0.6, more preferably 0.45 to 0.55.

In addition, in the above formula, α and β may be ethylene oxide (EO) or OH bonded thereto. Specifically, any one of the α and β is ethylene oxide (ethylene oxide; EO) is bonded.

The cationic cellulose polymer of the present invention may have a molecular weight of 300,000 to 2.9 million and a nitrogen content of 2.3 to 3.2% by weight based on the total weight of the polymer. The molecular weight of the cationic cellulose polymer may be preferably 600,000 to 2.5 million, more preferably 70,000 to 1.5 million. The nitrogen content of the cationic cellulose polymer may be preferably 2.5 to 3.0 wt%, more preferably 2.7 to 2.8 wt%, based on the total weight of the polymer.

When the molecular weight and nitrogen content of the cationic cellulose polymer are within the above ranges, the cumulative adsorption phenomenon of the hair may be prevented and a conditioning effect may appear on the hair. In an embodiment of the present invention (Examples 2 and 4 to 5), when the molecular weight of cellulose is 300,000 to 2.9 million and the nitrogen content is 2.3 to 3.2 wt%, even if the number of times of adsorption of the cationic polymer to the hair surface is increased The thickness of the cumulative adsorption layer decreased and remained constant. This is because adsorption is prevented by the mutual electrorepulsive force between the cationic polymer layer adsorbed to the hair and the cationic polymer to be adsorbed, while the portion adsorbed by a certain amount by molecular weight is treated as hydrophilic by the polymer adsorption layer with a high degree of cationization during the rinsing process. This is because it is easily soluble in water and washed off. In addition, it was confirmed that when the rinsing force was increased when the cationization degree and molecular weight were within the above range, the adsorption thickness decreased and fluctuated. On the other hand, when it was outside the range of the molecular weight and nitrogen content of the cationic cellulose polymer (Comparative Examples 8 to 14), it was observed that the adsorption thickness increased when the number of adsorption of the polymer was increased, that is, it was confirmed that cumulative adsorption occurred. , it was confirmed that the adsorption thickness did not change even when the rinsing force was increased, and cumulative adsorption continued to occur.

The present invention provides a composition for preventing cumulative adsorption comprising the cationic cellulose polymer as an active ingredient.

The composition may be treated with an anionic object, and the anionic object may be hair, skin or fibers.

When the composition is treated on the hair, skin, or fiber that is an anionic object, it is possible to prevent the cationic cellulose polymer from accumulating and adsorbing to the anionic object even during repeated use, thereby making the anionic object soft and smooth. can be wobbly

In addition, the present invention provides a composition for hair treatment or fiber treatment comprising the cationic cellulose polymer.

The cationic cellulose polymer is adsorbed to the hair surface, increasing the smoothness of the hair during rinsing and after drying. Through this, when the composition containing the cationic cellulose polymer of the present invention is used for hair treatment, in addition to the cleaning or styling function, which is the original function of a hair cosmetic, it exhibits a remarkable hair conditioning effect, thereby giving a high satisfaction to the user. In addition, the composition of the present invention can maintain the feeling of use by improving the physical state of the hair by supplying the smoothness of the hair even after repeated use.

When the composition of the present invention is used for fiber treatment, the skin irritation given by the conventional cationic surfactant used to give a fabric softening effect can be avoided, and the re-use of the polymer used for fiber treatment is caused by the cumulative adsorption to the fiber. It is possible to give a high satisfaction to the user by eliminating the stiff feeling of use of the fiber.

In the present invention, "prevention of accumulative adsorption" means that it is possible to prevent a phenomenon in which a polymer is accumulated and adsorbed on a surface to be used or a phenomenon in which a polymer is laminated when the polymer is repeatedly used. When the cumulative adsorption of the polymer is prevented, the degree of elasticity and smoothness of the target that can be used during the cumulative adsorption of the polymer is reduced, and the problem of stiffening can be solved so that the hair or fiber that can be used can become soft and flexible.

In the present invention, the composition may contain the cationic polymer in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight based on the total weight of the composition. When the content of the polymer is less than 0.01% by weight, the hair conditioning effect or the fabric softening effect is insignificant, and when it exceeds 10% by weight, there is a risk of inhibiting the formulation stability of the composition. This can be equally applied to the cosmetic composition for hair strengthening, elasticity enhancement or protection.

The composition may further include a cationic polymer other than the cationic cellulose polymer of the present invention, a cationic polymer that can be typically used in a composition for hair treatment or fiber treatment, a surfactant, or both.

The cationic polymer may be any one or more selected from the group consisting of a cellulose-based polymer, a guar-based polymer, and a synthetic material-based polymer. The cellulosic polymer may be JR125, JR400, JR30M, POLYQUAT-3000KC, LR-400R-LO, LR30M, Ucare LK, Catinal HC100, Catinal HC200, etc., and the guar-based polymer is guarhydroxypropyltrimonium chloride or hydroxypropyl guarhydroxypropyltrimonium chloride and the like. Synthetic polymers are polyquaternium-22, polyquaternium-47, polyquaternium-53, dimethyldiallylammonium chloride polymer, acrylamide-dimethyldiallylammonium chloride copolymer, polyvinylpyrrolidone (PVP)- It may be at least one selected from the group consisting of dimethylaminoethyl methacrylate copolymer, acrylic acid-dimethyldiallylammonium chloride copolymer, acrylamide-dimethylamino ethyl methacrylate methyl chloride copolymer, and trimethylaminoethyl methacrylate polymer. have.

The composition of the present invention may include a surfactant within a range that does not impair the purpose of the present invention for purposes such as increasing cleaning power.

As the surfactant, any one or more selected from the group consisting of anionic surfactants, amphoteric surfactants and nonionic surfactants may be used.

The anionic surfactant may be used without limitation as long as it is a component commonly used in hair compositions, and sodium lauryl sulfate, sodium laureth sulfate, ammonium lauryl sulfosuccinate, ammonium myreth sulfate, disodium laureth sulfosuccinate , disodium C12-C14 pareth-2 sulfosuccinate, or a mixture thereof and the like can be used.

In addition, the amphoteric surfactant may be any one or more selected from the group consisting of betaine, cocomidopropyl betaine, amidopropyl betaine and sulfobetaine, cocoamphocarboxy glycinate.

In addition, the nonionic surfactant may be any one or more selected from the group consisting of caprylyl / capryl glucoside, cocoglucoside, lauramide DA, cocamide DA, cocamide methyl EMA, and glyceryl monostearate. can

The cationic polymer included in the composition of the present invention may be included in an amount of 0.01 to 3% by weight, preferably 0.05 to 1% by weight, based on the total weight of the composition. The anionic surfactant may be included in an amount of 1 to 30% by weight, preferably 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, preferably 2 to 15% by weight, based on the total weight of the composition. When each of the components is included in the composition within the above range, the hair conditioning effect of the composition for the purpose of the present invention may be most excellently exhibited.

In addition, the composition of the present invention may further include additional adjuvants used in the art within a range that does not impair the purpose of the present invention in order to further enhance the conditioning effect. For example, water-insoluble non-volatile dimethicone, cyclomethicone, amination silicone, trimethylsilyl amodimethicone, or silicone components such as vinyl silicone and derivatives thereof, vegetable oils, vegetable oils, animal oils, Animal fats, hydrocarbon oils or synthetic ester oils and the like can be used. Liquid paraffin, isoparaffin or hydrogenated polydecene may be used as the hydrocarbon oil, and as the ester oil, isopropyl myristate, isopropyl palmitate, isostearyl isostearate or C12-15 alkyl benzoate may be used, but in this It is not limited.

In addition, the composition of the present invention may additionally contain fatty substances, organic solvents, solubilizers, thickeners, gelling agents, emollients, antioxidants, suspending agents, stabilizers, foaming agents, fragrances, surfactants, commonly used in hair and fabric softening compositions, Water, ionic or non-ionic emulsifiers, fillers, sequestering agents, preservatives, vitamins, blocking agents, wetting agents, essential oils, dyes, pigments, including any one or more selected from the group including hydrophilic or lipophilic active agents can do.

In addition, the composition of the present invention may additionally contain additives that provide beneficial properties to the human body. For example, washing, volume, tidying, protection, blocking, moisturizing, dyeing, coloring, bleaching, limiting, deodorizing, preserving, refreshing, hair removal, hair growth, anti-dandruff, hair loss prevention, wool, anti-inflammatory, fragrance, fragrance, whitening, Anti-aging, anti-wrinkle, convergence, relaxation, contraction, sebum suppression, keratin exfoliation, sterilization, anti-inflammatory, anti-seizure, deodorant, antihistamine, anti-seborrhea, blood circulation promotion, UV protection or skin metabolism promotion. Additives may be additionally included.

In addition to this, the composition of the present invention may further contain a preservative, a thickener, a viscosity modifier, a pH adjuster, a fragrance, a dye or a conditioning agent, which can be used as a component of the hair and fiber composition in addition, and these are commercially available It can be purchased and used. Examples of the preservative include benzoic acid and salts, methyl paraoxybenzoate, methylchloroisothiazolinone, or a mixture of methylisothiazolinone (trade name: Kathon CG, manufacturer: The Dow Chemical Company). As the thickener and viscosity modifier, hydroxypropylmethylcellulose, hydroxymethylcellulose, sodium chloride, ammonium chloride, propylene glycol, hexylene glycol or sodium xylene sulfonate, ammonium xylene sulfonate, and the like may be used. As the pH adjuster, citric acid, sodium hydroxide, or triethanolamine may be used. As the dye, a water-soluble tar dye may be used. And as the conditioning agent, animal and plant extracts, proteins and protein derivatives, higher fatty acids, etc. may be used.

The composition of the present invention may be prepared in the form of a general emulsified formulation or solubilized formulation.

In addition, the composition of the present invention can be prepared in any dosage form applicable to the scalp and fibers, such as liquid, cream, paste, or solid.

In addition, the composition of the present invention may be in any one formulation selected from the group including shampoo, hair conditioner, hair lotion, hair essence, hair gel, hair pack, patch and spray, laundry detergent, fabric softener, and the like.

The composition containing the cationic cellulose polymer of the present invention prevents the accumulation of adsorption of the polymer to the hair and fibers even when repeatedly used on hair and fibers, improves the smoothness of the hair, and reduces the stiffness of the hair and fibers. , the conditioning effect of hair and fibers is remarkably good. In addition, the composition comprising the cationic cellulose polymer of the present invention has excellent fabric softening effect when used for fiber treatment.

1 is a nanoscale image obtained by photographing the polymers of Comparative Example 8 and Example 2 by AFM.
2 is a graph showing the film thickness of the polymer of Comparative Example 8 and Example 2 according to the number of adsorption.
3 is a numerical view of the change in the adsorption thickness according to the increase in rinsing force by AFM. (A) is Comparative Example 10, (B) is the value obtained by changing the adsorption conditions of Example 2.

Hereinafter, examples and the like will be described in detail to help the 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 construed as being limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

manufacturing example One: cationic polymeric Produce

In the following Examples and Comparative Examples, raw materials synthesized by the present inventors were used and, if necessary, raw materials of Dow Chemical were used. In the polymerization process, the molecular weight was controlled by changing the content of ethyl cellulose, and the nitrogen content was adjusted by changing the amount of trimethylamine, thereby controlling the content of the degree of cationization.

A quaternized ammonium salt obtained by quaternizing hydroxyethyl cellulose with chlorohydroxypropyl trimethylamine was prepared. Specifically, sodium hydroxide and urea were contained at a concentration of 7.5:11:81.5 with respect to water as a solvent, and then hydroxyethyl cellulose was dissolved at a concentration of 2 wt%. Thereafter, the quaternary ammonium-based compound is additionally contained in 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 temperature (25, 45, 60 ° C) conditions to reform the chemical formula A quaternary cationic cellulosic polymer of 1 was prepared.

In addition, with reference to the reference (WO 2016085099 A1), EO addition or alkylation was performed to prepare a structure including an alkyl group. Specifically, gas phase polymerization using epoxide was performed to add ethylene oxide (EO) to the α and β positions in the glucose ring of the cationic cellulose polymer, and the temperature and pressure were applied after spraying the reactants in the chamber. EO was added to proceed with the reaction. In the case of alkylation, the reaction was carried out so that a desired alkyl group could be added using a reactant having a terminal functional group of halohydrin, aldehyde, or epoxide, and the OH groups at the α and β positions in the glucose ring were substituted with alkyl. .

Experimental example 1: according to substitution polymer Cumulative adsorption thickness change during adsorption

In order to confirm the cumulative adsorption properties of the polymer according to the substituents at the α and β positions in the glucose ring of the cationic polymer and the effect of rinsing on it, C2 (α) and C3 (β) were substituted in the glucose ring as shown in Table 1 below. Polymer samples of Examples and Comparative Examples were prepared. In Comparative Example 1, distilled water was used as a control. The cationic cellulose polymers of Examples and Comparative Examples had a molecular weight of 800,000 and were synthesized using a nitrogen content (wt%) of 2.7%.

polymer substitution sample Example 1 Example 2 Example 3 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 substitution α β α β α β α β α β α β α β α β α β substitution
group EO OH EO
2nd OH EO
2nd
More than EO
1st
More than OH OH C5
Below OH C5
More than
C10
less alkyl OH C10
More than
C18
less alkyl OH C18
more than alkyl OH quaternary ammonium EO

In order to evaluate the adsorption state of cationic polymers, the method used by many companies including Dow Corning, a raw material for conditioning agent, is used to evaluate the adsorption status of cationic polymers, which generally have an anionic charge (Zeta potential) of several tens of mV, similar to that of hair and wool. Mica was selected as a substrate, and a cationic polymer was adsorbed to the mica substrate to determine the adsorption properties of the polymer. Even for the same person, there are many variables such as hair cuticle spacing, cuticle thickness, cuticle state, hair hydrophobicity, hair thickness, etc. Therefore, in this experiment, a mica disk was selected as a substrate and the cumulative adsorption was evaluated by measuring the adsorption thickness of the cationic polymer.

A 12 mm diameter mica disk (TED PELLA, Canada) was used as an adsorption target. Using 10 ml of distilled water containing 0.5% of the polymer, the polymer was adsorbed to only half of the mica disk, and then the polymer was left standing and washed with distilled water. The amount of polymer adsorption is determined by electrical attraction and repulsion between the polymer and the mica and the adsorbed polymer on the mica. And since desorption proceeds by the hydrophilicity of the polymer and water, a change in the amount of polymer does not affect the amount of adsorption. Therefore, 0.5%, which is the amount of polymer typically used in shampoo, was selected as the experimental condition.

The boundary between the adsorbed polymer layer and the mica bottom was shown as a topography of the contact mode of the tip (NSC 36C, Mikro Masch, Germany) by atomic force microscopy (hereinafter, AFM, Model XE-100 of Park Systems, Korea). The thickness was evaluated as follows, and the average thickness is shown in Table 2.

Comparative Example 1 of Table 2 is a measurement of the thickness of mica dipped only in distilled water containing no polymer. As can be seen from the results of Comparative Example 1, it can be seen that the cumulative adsorption is due to the polymer adsorption, and the thickness difference is the difference from the polymer adsorption amount.

Comparative Example 2 is a cellulose polymer having a molecular weight of 800,000, a nitrogen content of 2.7% by weight, α is an OH group and β is an OH group in Formula 1, Comparative Example 3 has a molecular weight of 800,000 and a nitrogen content of 2.7% by weight, and Formula 1 In α is an alkyl group with 5 or less carbon atoms and β is an OH group.

Comparative Example 4 is a cellulose polymer having a molecular weight of 800,000, a nitrogen content of 2.7% by weight, α is an alkyl group having 5 to 10 carbon atoms in Formula 1, and β is an OH group, Comparative Example 5 has a molecular weight of 800,000, nitrogen The content is 2.7 wt%, and in Formula 1, α is an alkyl group having 10 or more and 18 or less carbon atoms, and β is an OH group.

Comparative Example 6 is a cellulose polymer having a molecular weight of 800,000, a nitrogen content of 2.7% by weight, α is an alkyl group having 18 or more carbon atoms in Formula 1, and β is an OH group, Comparative Example 7 has a molecular weight of 800,000 and a nitrogen content of 2.7% by weight %, and in Chemical Formula 1, α is quaternary ammonium and β is an OH group, which is a cellulosic polymer. The quaternary ammonium is the same as quaternary ammonium linked to the ethylene oxide (EO) group of the glucose ring C5 of Chemical Formula 1.

Example 1 is a cellulose polymer having a molecular weight of 800,000, a nitrogen content of 2.7% by weight, in Formula 1, α is an ethylene oxide (EO) group, and β is an OH group, Example 2 has a molecular weight of 800,000 and a nitrogen content of 2.7% by weight %, and in Formula 1, α is a divalent or higher ethylene oxide (EO) group, and β is an OH group.

Example 3 is a cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7 wt%, in Formula 1, α is an ethylene oxide (EO) group having a divalent or higher value, and β is an EO group having a monovalent or higher value.

Thickness measurement as a result of polymer conversion, in μm number of adsorption Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 0 0 0 0 0 0 0 0 0 0 0 One 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

From the results shown in Table 2, it can be seen that the adsorbed thickness in Examples 1 to 3 is constant. Through this, it can be seen that when EO is added to the place bonded to the 2nd or 3rd carbon of the glucose ring unit in the cellulose skeleton, there is an effect of preventing the accumulation of adsorption.

In the above example, it can be seen that the thickness of the adsorption layer increases when the adsorption proceeds repeatedly from 1 to 3 times, which can be seen as the continuous adsorption of the cationic polymer as a single layer in the space above the negatively charged surface. . From the 3rd and 4th times, the adsorption thickness of the cationic polymer decreased, indicating that the anion surface was sufficiently covered by the adsorption of the cationic polymer (full surface coverage). When a cationic polymer is adsorbed on a single layer having an overall negative charge, the adsorption power is lowered due to the cation repulsion with the already adsorbed polymer, so the polymer in the adsorption layer on the single layer is washed down by the hydrophilic power with water during the rinsing process. can be known

In Comparative Examples 2 to 6, it was observed that the adsorption thickness of the adsorption layer increased as the number of adsorption increased. , it seems that the rinsing power is relatively lowered in the binding relationship with water, so that the cumulative adsorption phenomenon has progressed. In fact, as in Comparative Example 6, it can be seen that as the length of the alkyl group increases, the hydrophilicity with water molecules decreases as the hydrophobicity increases, so that the cumulative adsorption phenomenon occurs.

In Comparative Example 7, it can be seen that the thickness of the adsorption layer is significantly reduced as the number of adsorption increases. This can be seen as a phenomenon in which the adsorbed cationic polymer is washed off by binding with water molecules during the rinsing process after the polymer is adsorbed to the hair surface. have. That is, when two or more ammonium is present in the quaternary cellulose, it can be seen that the rinsing force is excessively increased, thereby preventing the adsorption of the polymer.

Experimental example 2: molecular weight and in the degree of cationization followed polymer Accumulation upon adsorption adsorption layer thickness change

In order to confirm the effect of molecular weight on the adsorption properties of cationic polymers, polymer samples of Examples and Comparative Examples having molecular weight and nitrogen content (wt%) as shown in Table 3 below were prepared. In Comparative Example 8, Dow Chemical's Ucare polymer JR125 was used, and the polymer of Comparative Example 9 was prepared. As the polymer of Comparative Example 10, Ucare polymer JR30M of Dow Chemical was used, and the polymers of Comparative Examples 11 to 14 were prepared.

Samples for evaluation of cumulative adsorption layer thickness sample Example 2 Example 4 Example 5 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 polymer cellulose cellulose cellulose cellulose cellulose cellulose cellulose cellulose cellulose cellulose Molecular Weight 800,000 1.8 million 2.5 million 250,000 250,000 800,000 1.8 million 2.5 million 3 million 3 million N% 2.7 2.7 2.7 1.8 2.7 1.8 1.8 1.8 1.8 2.7

Comparative Example 8 used a cationic cellulose polymer having a molecular weight of 250,000 and a nitrogen content of 1.8 wt%, and Comparative Example 9 used a cationic cellulose polymer having a molecular weight of 250,000 and a nitrogen content of 2.7 wt%.

Comparative Example 10 used a cationic cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 1.8 wt%, and Comparative Example 11 used a cationic cellulose polymer having a molecular weight of 1.8 million and a nitrogen content of 1.8 wt%.

Comparative Example 12 used a cationic cellulose polymer having a molecular weight of 2.5 million and a nitrogen content of 1.8 wt%, and Comparative Example 13 used a cationic cellulose polymer having a molecular weight of 3 million and a nitrogen content of 1.8 wt%.

Comparative Example 14 used a cationic cellulose polymer having a molecular weight of 3 million and a nitrogen content of 2.7 wt%, and in Example 2, a cationic cellulose polymer having a molecular weight of 800,000 and a nitrogen content of 2.7 wt% was used.

Example 4 used a cationic cellulose polymer having a molecular weight of 1.8 million and a nitrogen content of 2.7 wt%, and Example 5 used a cationic cellulose polymer having a molecular weight of 2.5 million and a nitrogen content of 2.7 wt%.

Cumulative adsorption layer thickness evaluation result, unit μm number of adsorption Example 2 Example 4 Example 5 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 0 0 0 0 0 0 0 0 0 0 0 One 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

From the results shown in Table 4, it can be seen that the adsorbed thickness is constant in Example 2 and Examples 4 and 5. Through this, it can be confirmed that the cumulative adsorption phenomenon is prevented by adjusting the molecular weight and nitrogen content (cationization degree). Referring to Comparative Examples 8 to 14, it can be seen that the adsorption thickness increased when the number of times of polymer adsorption was increased ( FIGS. 1 and 2 ).

It seems that a certain amount of the polymer is uniformly adsorbed when it is adsorbed to the surface of the hair, which is an anion with a high degree of cationization. In fact, in Examples other than Example 2 and Examples 4 and 5, it was also found that the thickness layer of the polymer was not homogeneous. The reason that the adsorption thickness increased during adsorption 1 to 2 in Examples is due to continued adsorption of the cationic polymer to the hair surface. The thickness decreases and becomes constant from the third cycle, which prevents adsorption by the mutual electrorepulsive force between the cationic polymer layer adsorbed on the hair and the cationic polymer to be adsorbed, while the portion adsorbed by a certain amount by molecular weight is rinsed during the rinsing process. It seems to occur because the polymer adsorption layer with high cationization degree is hydrophilic and is washed away by binding with water. As a result, the conditions of Example 2 and Examples 4 to 5 of cellulose molecular weight of 800,000 to 2.5 million and nitrogen content of 2.7 wt% seem to prevent the cumulative adsorption phenomenon.

Experimental Example 3: Cumulative adsorption layer thickness change according to rinsing force

In order to confirm whether the cumulative adsorption prevention phenomenon shown in Table 4 is due to the rinsing force, an experiment was conducted to confirm the adsorption thickness by changing the rinsing force while adsorbing the polymer under the adsorption conditions of Comparative Examples 10 and 2 as shown in Table 5. did. In the case of Comparative Example 10 and Example 2, the molecular weight is the same as 800,000, but the nitrogen content is different from 1.8 and 2.7%.

Samples for evaluation of cumulative adsorption layer thickness Experimental division Experiment #1 Experiment #2 Experiment #3 Experiment #4 Experiment #5 Experiment #6 Experiment #7 Experiment #8 nitrogen content 1.8% (Comparative Example 10) 1.8% (Comparative Example 10) 1.8% (Comparative Example 10) 1.8% (Comparative Example 10) 2.7% (Example 2) 2.7% (Example 2) 2.7% (Example 2) 2.7% (Example 2) rpm 0 20 40 60 0 20 40 60

Experiments #1 to #4 were tested with the polymer of Comparative Example 10, and Experiments #5 to #8 were tested with the polymer of Example 2. All experiments were carried out by adsorption to the mica disk and then washed by standing still. After changing the rinsing force by putting the Petri dish in a shaker (Jeio Tech, SI-900R, Korea) and shaking at 20, 40, 60 rpm to apply the rinsing force, The thickness of the adsorption layer was measured and indicated as shown in Table 6.

Cumulative adsorption layer thickness evaluation result, unit μm Experimental division Experiment #1 Experiment #2 Experiment #3 Experiment #4 Experiment #5 Experiment #6 Experiment #7 Experiment #8 0 0 0 0 0 0 0 0 0 One 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

The thickness change of Table 6 is shown as a graph in FIG. 3 . 3A shows Experiment #4 in Experiment #1, and FIG. 3B shows Experiment #8 in Experiment #5. When (A) with a relatively low nitrogen content is compared with (B) with a high nitrogen content, in (A), a cumulative adsorption phenomenon occurs. However, as in (B), when cumulative adsorption was prevented, increasing the rinsing force decreased the adsorption thickness and showed fluctuating results.

Combining the above results, it is shown that the cumulative adsorption prevention phenomenon of the adsorption layer is related to the high nitrogen polymer, and the high degree of cationization reflected in the high nitrogen portion and the hydrophilicity acting with water play a decisive role in this effect .

In other words, it was found that the cumulative adsorption phenomenon could be prevented by adsorbing the high nitrogen content polymer to utilize the rinsing power.

Experimental Example 4: Cumulative adsorption layer thickness change during polymer adsorption according to the degree of cationization

Since it was confirmed that the cumulative adsorption phenomenon did not occur in Example 2 and Examples 4 and 5 of Table 3, the polymer was prepared by applying various degrees of cationization based on the molecular weight of 800,000 of the cationic polymer of Example 2 as shown in Table 7 did. The degree of cationization depends on the nitrogen content.

Samples for evaluation of the cumulative adsorption layer thickness according to the degree of cationization sample Example 6 Example 7 Comparative Example 15 Comparative Example 16 Comparative Example 17 polymer cellulose cellulose cellulose cellulose cellulose Molecular Weight 800,000 800,000 800,000 800,000 800,000 N% 2.3 3.0 1.7 2.0 3.3

For the samples in Table 7, the adsorption thickness was evaluated according to the degree of cationization, and the results are shown in Table 8 below.

Adsorption thickness evaluation result according to the degree of cationization (unit: ㎛) number of adsorption Example 6 Example 7 Comparative Example 10 Comparative Example 15 Comparative Example 16 Comparative Example 17 0 0 0 0 0 0 0 One 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

As shown in Table 8, in Comparative Examples 10, 15, and 16, the adsorption thickness increases as the number of adsorption increases, and the degree of cationization due to the electrorepulsive force occurring during adsorption is not sufficient, so cumulative adsorption It can be seen that a phenomenon is occurring.

In the case of Examples 6 to 7, there was no increase in the adsorption thickness according to the increase in the number of adsorption, and it was confirmed that the cumulative adsorption phenomenon was prevented when the nitrogen content was 2.3 to 3.2 wt% when the molecular weight was 800,000. From this, it can be seen that in a low molecular weight state, the degree of cationization must be at a certain level to suppress additional adsorption by the electrorepulsive force.

However, in the case of Comparative Example 17, in which the nitrogen content, which determines the degree of cationization, is greater than 3.2% by weight relative to the weight of the polymer, the cumulative adsorption phenomenon is prevented, but the adsorption layer is rather decreased as the number of adsorption increases. was found to interfere with adsorption It is judged that desorption occurs due to hydrophilicity with water during rinsing because the degree of cationization is too high.

Experimental Example 5: Cumulative adsorption layer thickness change during polymer adsorption according to polymer base

For the evaluation of the thickness of the cumulative adsorption layer according to the polymer base, the cumulative adsorption phenomenon was observed for the cellulose and other polymers described in Table 9 below, and the results are shown in Table 10 below.

In Comparative Example 18, Ashland's N-Hance CCG45, which is guarhydroxypropyltrimonium chloride, was used, and in Comparative Example 19, hydroxypropyl guarhydroxypropyltrimonium chloride, Ashland's OaSense Care CT400, was used. was used.

In Comparative Examples 20 and 21, ethyltrimonium chloride methacrylate/propyltrimonium acrylamide/dimethylacrylamide copolymer synthetic polymer of Patent Registration No. 10-1291693 was used.

Samples for evaluation of cumulative adsorption through polymer bases sample Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 polymer guar guar synthesis synthesis Molecular Weight 800,000 800,000 800,000 800,000 N% 1.4 2.7 1.4 2.7

Cumulative adsorption evaluation result through polymer base (unit: μm) number of adsorption Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 0 0 0 0 0 One 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

As shown in Table 10, no cumulative adsorption prevention was observed in polymers other than cellulose. The chemical structure is that cellulose has a linear ethyl cellulose structure, but guar polymer has a branched structure, so the desorption effect that occurs during rinsing due to the hydrophilicity of guar polymer after adsorption is significantly lowered, so that the cumulative adsorption phenomenon cannot be prevented. In the case of synthetic polymers, the binding position of cationic nitrogen is different, so it is interpreted that the repulsive force that occurs during adsorption is different than that of cellulose.

Experimental Example 6: Sensory evaluation of rinsing and conditioning according to the polymer

A shampoo composition was prepared in a conventional manner according to the prescription shown in Table 11 below.

Shampoo prescription Ingredients Weight ratio (%) polymer 0.5 Sodium Laureth Sulfate 8 Cocamidopropyl Betaine 4.5 EDTA 4Na, hydrous citric acid 0.1 other ingredients 16 Purified water Balance (to 100)

Since the cellulosic polymer has excellent solubility, after adding the polymer, a surfactant was sequentially added to dissolve it, and then EDTA·4Na and hydrous citric acid were added to neutralize the pH. As for the other ingredients, preservatives, flavoring agents, dispersants, viscosity adjusting agents and pH adjusting agents were added.

1g hair tress was placed in 100 mL of the 10% dilution of the shampoo and stirred at 150 rpm for 5 minutes, followed by rinsing for 2 minutes with 4 ml/sec flowing water, repeated 5 times. A 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 males and females each, and the conditioning effect of the hair after shampooing was evaluated based on the freshness of the following evaluation criteria. The results are shown in Table 12 below as average values.

Experiment #9 is the result of treatment with sodium lauryl sulfate, an anionic surfactant without treating the polymer, and Experiment #10 was applied to hair that had accumulated adsorption by shampooing using the cationic cellulose polymer of Comparative Example 10. Experiment #11 applied the polymer according to the present invention (Example 2) as a conditioning polymer.

Evaluation criteria- Measure the order in which the hair feels fresh, and the opposite is stiff.

(5: very good); (4: Excellent); (3: Normal); (2: bad); (1: very bad)

sensory evaluation Experimental division Experiment #9 Experiment #10 Experiment #11 when wet 1.3 1.9 3.7 after dry 2.1 1.6 4.2

As shown in Experiment #11 of Table 12, it can be seen that the cumulative adsorption-preventing polymer gives freshness and breaks away from the existing stiff sensibility.

Experimental Example 7: Frictional force evaluation

The conditioning effect of the cationic polymer was applied to the shampoo and the friction force was quantified by device evaluation.

The shampoo composition of Table 11 was put into the Burex hair tress in an amount of 10% by weight based on the weight, bubbled for 15 seconds, rubbed for 20 seconds, rinsed in running tap water at 37°C for 15 seconds, and then the hair was wiped with a towel to remove moisture. After subtraction, the friction force was evaluated using an MTT 175 Miniature Tensile Tester (DiaSTRON, GB).

For another hair, rinse the shampoo-treated hair for 2 minutes, dry it with a dryer for 2 minutes, maintain it at 25° C. in a constant temperature and humidity room with 50% humidity for one day, make the moisture inside the hair constant, and then use the friction force in the same constant temperature and humidity room. was measured and the results are shown in Table 13 below.

At this time, the hair tress was washed with sodium lauryl sulfate, an anionic surfactant, and the value of the friction force of the hair was calculated by comparing the difference with the measured value using this as a reference value.

Change in frictional force on the surface of hair according to one use (%) Experimental division Experiment #12
(Polymer of Comparative Example 10) Experiment #13
(Polymer of Example 2) when rinsing 21 55 after dry 13 21

When looking at the results measured in Table 13, the shampoo to which the polymer presented in the present invention is applied shows a result of rinsing quickly during rinsing, and the friction force is remarkably reduced even after it dries, showing that it promotes a smooth conditioning effect. In addition, as can be seen from the above examples, the polymer prepared in the present invention provides a cumulative absorption prevention effect when applied as a conditioning agent, thereby solving the problem of cumulative absorption in which a stiff feel is felt, thereby giving freshness to the hair and at the same time It was confirmed that it is a component of an excellent hair conditioning cosmetic composition.

Subsequently, in order to check whether the cumulative adsorption prevention phenomenon according to repeated use is applied to hair and at the same time improves the stiffness caused by the accumulation prevention phenomenon, the frictional force was evaluated as shown in Table 14 by shampooing 60 times.

Change in hair surface friction force after 60 uses (%) Experimental division Experiment #14
(Polymer of Comparative Example 10) Experiment #15
(Polymer of Example 2) when rinsing 20 56 after dry 4 21

The decrease in the frictional force change of the hair surface in Experiment #14 that occurs when the shampoo according to the prescription of Table 11 is repeatedly washed on the hair can be understood as a decrease in smoothness due to the texture of the polymer accumulated on the hair during repeated use. In Experiment #15, the effect of no change in frictional force even after repeated washing and adsorption reflects no change in the polymer layer.

Claims (12)

As a cationic cellulose polymer represented by the following formula (1), a cationic cellulose polymer having a nitrogen content of 2.3 to 3.2% by weight based on the total weight of the polymer, and a molecular weight of 300,000 to 2.9 million Da:
[Formula 1]

In the above formula, α and β are ethylene oxide (EO) or OH bonded, and any one of α and β is ethylene oxide (EO) bonded,
x is 1 to 10; When n is 1, y is 0.3 to 0.7.
delete delete The cationic cellulosic polymer according to claim 1, wherein the molecular weight is between 600 and 2.5 million.
The cationic cellulosic polymer according to claim 1, wherein the nitrogen content is 2.5 to 3.0% based on the total weight of the polymer.
delete delete delete delete delete delete delete

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