KR100506422B1 - Hair Conditioning and Styling Composition - Google Patents

Abstract

At least one polymerizable with free radicals, having substantially the same rigidity as a material having a general setting function, having no hair stickiness or stiffness after application, and having no negative effect on the hair properties after drying, and combing easily. Vinyl monomer A, at least one reinforcing monomer copolymerizable with monomer A, a monomer B selected from the group consisting of a polar monomer and a macromer and a molecular weight of 1,000 to 50,000, and a molecular weight of 10,000 including the polymeric monomer Twin C represented by the formula (1) A styling composition comprising a silicone-containing copolymer having a vinyl polymeric backbone grafted with a divalent siloxane polymeric moiety and a carrier suitable for application to the hair.

[Formula 1]

X (Y) _n Si (R ¹ ) ₂ (Z) _m (Y) _n X

In Formula 1, X is a vinyl group copolymerizable with monomers A and B, Y is a divalent bonding group, R ¹ is hydrogen, lower alkyl having 1 to 5 carbon atoms, aryl, alkoxy, alkylamino or hydroxyl group, Z is a monovalent siloxane polymeric moiety that has a number average molecular weight of at least about 500 and is substantially non-reactive under copolymerization conditions, after being copolymerized, linked to the vinyl polymeric backbone of monomer A or monomer B, n is 0 or 1, m Is an integer of 1 to 3.

Description

Hair Conditioning and Styling Composition

[Industrial use]

FIELD OF THE INVENTION The present invention relates to hair conditioning and styling compositions, and more particularly to hair applied hair conditioning and styling compositions that improve hair conditioning and style retention features and maintain hair in a non-sticky, natural feel. will be.

[Prior art]

The desire to keep hair in a particular form has been widely demanded to date. This style maintenance can generally be accomplished in two ways: permanent chemical change and temporary change of the hairstyle. The permanent permanent chemical change is the chemical change of the hair through the perm, the temporary change being obtained by applying the composition to moist hair after shampoo and / or conditioning and before drying and / or setting. In general, the material used to fix the hair in a fixed form in a temporary change is an adhesive resin or gum, and is provided in the form of mousse, gel, lotion or spray. However, the method of changing the hair using such a composition is cumbersome to apply the setting composition after shampooing / conditioning, and since the adhesive resin material is applied to the hair, the hair tends to become sticky or stiff after application. After drying, it damages the hair properties such as the ease of combing, and it is difficult to change the shape of the hair again unless the styling composition is applied again.

Overcoming these shortcomings, the hair composition does not stiffen or become sticky even after application, and does not adversely affect hair properties after drying, so it is easy to comb and has a hair composition that can be restyled many times without reapplying the composition. The research to obtain has been conducted, and as a result, a hair composition is provided that can satisfy this purpose.

In some instances, a rinse-off hair protection composition capable of styling or conditioning hair is disclosed in U.S. Patent Application Nos. 07 / 551,118 (Bolich, July 1990), 07 / 551,119 (1990). (Norton, July) and 07 / 551,120 (Russell, July 1990). The patent applications describe hair protection compositions comprising silicone macromer-containing hairstyle polymers that have gel-like properties based on hydrophobically modified water soluble polymers and impart conditioning effects to hair. In addition, silicone macromer-containing polymers, as well as other rinse-off hair protection compositions containing them, are described in U.S. Patent Application Nos. 07 / 505,755 (April 1990, Bolwich, Torison) and 07 / 505,760 (1990). April, Volich, Gabe).

The compositions described in this patent application can provide excellent hair styling and conditioning effects, but the silicone macromer-containing polymers essential to the composition are silicone macromers with one vinyl group, which are generally used to impart setting functions to hair so far. There is a disadvantage in that the effect of maintaining the hair in a constant form is reduced because it is softer than a material such as resin or gum used.

Accordingly, the present invention relates to a hair composition that provides effective hair conditioning and styling retention properties, having substantially the same rigidity as a material having a general setting function, and not causing the hair to become sticky or stiff after application and negative to hair properties after drying. It is an object of the present invention to provide a hair application composition comprising a silicone macromer-containing copolymer that is easy to comb without affecting and that can be restyled multiple times without reapplying the styling composition.

Another object of the present invention is to formulate a hair application composition that provides conditioning and style retention properties from a single composition.

[Means for solving the problem]

In order to achieve the above object, the present invention provides a composition comprising (a) at least one vinyl monomer A polymerizable with free radicals, 0 to 80% by weight, and at least one reinforcing monomer copolymerizable with monomer A in the group consisting of a polar monomer and a macromer. Grafted with selected monomers B, from 0 to 80% by weight and molecular weight from 1,000 to 50,000 and polymeric monomer Twin C represented by Formula 1, from 0.01 to 50% by weight and from 10,000 to 1,000,000 with a divalent siloxane polymeric moiety Provided is a hair application composition comprising a silicone-containing copolymer with a vinyl polymeric backbone, 0.01 to 30.0 weight percent and (b) a carrier suitable for application to hair, 0.5 to 99.5 weight percent.

[Formula 1]

X (Y) _n Si (R ¹ ) ₂ (Z) _m (Y) _n X

In Formula 1, X is a vinyl group copolymerizable with monomers A and B, Y is a divalent bonding group, R ¹ is hydrogen, lower alkyl having 1 to 5 carbon atoms, aryl, alkoxy, alkylamino or hydroxyl group, Z is a monovalent siloxane polymeric moiety that has a number average molecular weight of at least about 500 and is substantially non-reactive under copolymerization conditions, after being copolymerized, linked to the vinyl polymeric backbone of monomer A or monomer B, n is 0 or 1, m Is an integer of 1 to 3.

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

Compositions of the present invention have a hair styling having a molecular weight of about 10,000 to about 1,000,000, a Tg of at least -10 ° C and a silicone macromer having a molecular weight of about 1,000 to 50,000 covalently bonded to the organic oligomer unit section of the non-silicone polymer backbone / Conditioning copolymer, about 0.01 to 30% by weight, a carrier suitable for application to the hair, about 0.5 to 99.5% by weight and any additives corresponding to the remaining amount.

The composition of the present invention may be in a conventional form including, but not limited to, shampoos, conditioners, rinses, hair sprays, lotions, mousses, hair tonics and gels.

The silicone-containing copolymers, carriers and optional additives included in the compositions of the present invention are as follows, respectively. Hereinafter, unless stated otherwise in the present invention, all percentages and percentages refer to weight percentages and weight ratios.

Silicone-containing copolymer

The composition of the present invention comprises about 0.01% to 30%, preferably about 0.5% to 10%, of a specifically defined silicone-containing copolymer. The weight average molecular weight of the silicone-containing copolymer is about 10,000 to about 1,000,000, preferably about 3,000 to about 300,000, and Tg is at least about -20 ° C, preferably at least -10 ° C. When transition occurs in a given polymer, "Tg" means the glass transition temperature of the non-silicone backbone, and "Tm" means the crystalline phase melting point of the non-silicone backbone.

In a broad sense, silicone-containing copolymers include copolymers of silicone-containing monomers and non-silicone adhesive polymers. When the silicone-containing copolymer is formulated into a hair protection composition and dried, the copolymer phase is divided into a discontinuous phase comprising a silicone macromer such as polydimethylsiloxane and a continuous phase comprising a main chain of a non-silicone adhesive polymer. When separated, these phase separation properties provide a particular orientation of the polymer in the hair and thus provide desirable hair conditioning and hair fixation properties.

Some examples of useful copolymers and methods for their preparation are described in US Pat. Nos. 4,693,935 (Mazrek, September 1987) and 4,728,571 (Clemens, March 1988), and also referred to as "Principles of Polymerization". (Gerorge Odian, John Wiley & Sons, 2nd edition, p492).

Silicone-containing copolymers of the present invention include monomers A, B and Twin C, generally from about 0% to 80%, preferably from about 10% to 80%, more preferably relative to the total amount of all monomers in the copolymer. Is about 10% to 70% monomer A, about 0% to 80%, preferably about 7.5% to 80% monomer B and about 0.01% to 50%, preferably about 2% to 25% monomer Twin Contains C.

Monomer A is a monomer or monomers which are hydrophobic and contain at least one vinyl group which is free radically polymerizable. Typical examples of monomer A include vinyl chloride, vinylidene chloride, vinyl propionate, α-methylstyrene, tert-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyl toluene, acrylonitrile, ethoxy ethyl acryl Alcohols of about 1 to 18 carbon atoms, such as methanol, ethanol, methoxy ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol Tert-butanol such as 2-methyl-2-propanol, cyclohexanol, neodecanol, 2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptane Ol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol , 1-octadecanol, etc.) acrylic acid or methacrylic acid Le, styrene, polystyrene macromer, a vinyl acetate, and mixtures thereof. Preferred monomers A are n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, acrylonitrile, Methoxy ethyl acrylate and mixtures thereof.

Monomer B can optionally be used, which is hydrophilic, is one or more reinforcing monomers copolymerizable with monomer A and imparting hydrophilicity and setting force, from a group consisting of polar monomers and macromers having a Tg or Tm of at least about −20 ° C. Is selected. Typical examples of monomer B include tert-butyl acrylamide, maleic acid, maleic anhydride and its half esters, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, hydroxyethyl methacrylate, acrylic acid, methacrylic acid, Vinyl ethers such as N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethyl aminoethyl methacrylate, methacrylamide, diallyldimethyl ammonium chloride, vinyl pyrrolidone, methyl vinyl ether, maleimide, Vinyl pyridine, vinyl imidazole, polar vinyl heterocycle, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl caprolactam and mixtures thereof prepared by hydrolyzing vinyl acetate after polymerization. Preferred monomers B include vinyl pyrrolidone, acrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate and mixtures thereof.

Monomer Twin C is a compound comprising two vinyl groups represented by the following formula (1) having a weight average molecular weight of about 1,000 to 50,000, preferably about 5,000 to 40,000, and most preferably 10,000 to 20,000.

[Formula 1]

X (Y) _n Si (R ¹ ) ₂ (Z) _m (Y) _n X

In Formula 1, X is a vinyl group copolymerizable with monomers A and B, Y is a divalent bonding group, R ¹ is hydrogen, lower alkyl having 1 to 5 carbon atoms, aryl, alkoxy, alkylamino or hydroxyl group, Z is a monovalent siloxane polymeric moiety that has a number average molecular weight of at least about 500 and is substantially non-reactive under copolymerization conditions, after being copolymerized into the polymeric backbone of monomer A or monomer B, n is 0 or 1, m is It is an integer of 1-3.

The monomer Twin C is preferably a compound represented by the formulas (2), (3) and (4).

[Formula 2]

[Formula 3]

X-Si (R ² ) ₂ -Z _m -X

[Formula 4]

In the above formula, m is 1, 2 or 3, preferably 1, p is 0 or 1, q is an integer of 0 to 2, R ² is lower alkyl, aryl, alkoxy, alkyl having 1 to 5 carbon atoms An amino or hydroxyl group, preferably a lower alkyl group having 1 to 5 carbon atoms, and X is Wherein R ³ is hydrogen or a -COOH group, preferably hydrogen, and R ⁴ is preferably hydrogen, methyl or methyl as -CH ₂ COOH. Z is also And r is an integer from about 5 to 700, with about 250 being preferred.

The monomer Twin C contains two vinyl groups, and thus crosslinks them to prepare a hard silicone-containing copolymer as compared to the silicone-containing copolymer having a pendant bond using the conventional vinyl group C monomer. Can be.

By appropriately selecting and combining the monomers A, B, and Twin C as described above, the copolymer may be included under optimum conditions within a specific carrier. For example, the polymer soluble in the aqueous formulation may contain about 0% to 80%, preferably 10% to 70% monomer A, about 7.5% to 80%, preferably about 30% to 70% monomer B and It has a composition of monomeric Twin C of about 2% to 25%. In addition, the dispersible polymer is about 0% to 80%, more preferably about 10% to 70% monomer A, about 20% to 80%, more preferably about 20% to 60% monomer B and about 2 It has a composition of monomer Twin C of% to 25%. In this case, as the content of the monomer B is increased, water solubility may be imparted to the copolymer.

Polymers having the following constitution are more preferred for use in the present invention.

Polymer 1. Acrylic acid: vinyl pyrrolidone: polydimethylsiloxane macromer (molecular weight 8,000) = 10: 70: 20

Polymer 2. N, N-dimethylacrylamide: isobutyl methacrylate: polydimethylsiloxane macromer (molecular weight 20,000) = 20: 60: 20

Polymer 3.N, N-dimethylacrylamide: vinyl pyrrolidone: 2-ethylhexyl methacrylate: polydimethylsiloxane macromer (molecular weight 30,000) = 10.5: 61: 3.5: 25

(The above ratios are not necessary for the finished polymer, but for the amount of reactants added to the polymerization.)

Polymers 1, 2 and 3 described above are prepared in the following manner. In the methods described below, the degassing method, gas selection, initiator type selection, conversion range, reaction load, and the like may be modified as necessary. The initiators and solvents are selected according to the specific monomers to be used, since they exhibit different solubility and different reactivity to specific initiators depending on the monomers used during the reaction.

Polymer 1: Acrylic acid, vinyl pyrrolidone and polydimethylsiloxane macromer (molecular weight 8,000) are added to the flask at a ratio of 10:70:20 and ethyl acetate is added to bring the final monomer concentration to 40%. To this is added an initiator, benzoyl peroxide, in an amount corresponding to 0.5% by weight of the monomer, the vessel is evacuated and backfilled with nitrogen. The mixture is heated to 60 ° C., stirred at this temperature for 48 hours, then cooled to room temperature to terminate the reaction, the reaction mixture is poured into a Teflon-coated pan and placed in a vacuum oven to dry ethyl acetate.

Polymer 2: N, N-dimethylacrylamide, isobutyl methacrylate and polydimethylsiloxane macromer (molecular weight 20,000) were added to a reaction vessel equipped with a temperature probe, reflux cooler, inlet port and argon sparger at 20:60: It is added at a reaction ratio of 20 and toluene is added so that the final monomer concentration is 20% by weight. The reaction vessel is heated to 60 DEG C in a water bath with sparging argon for 1 to 2 hours, and an initiator, azobisisobutyronitrile, corresponding to an amount of 0.25% by weight of the monomer weight is added. The temperature of the reaction vessel is maintained at 60 ° C., the solution is mixed with argon flowing at a sufficient rate, and the reaction is visually monitored to ensure that phase separation of the reactants does not occur during the polymerization. If a particular turbidity is observed, it is sufficiently heated to add degassed toluene to remove the turbidity. While continuing to monitor the reaction, the reaction is carried out for 4 to 6 hours, and after completion of the reaction, purification is performed in the same manner as in Polymer 1.

Polymer 3: N, N-dimethylmethacrylamide, vinyl pyrrolidone, 2-ethylhexyl methacrylate and polydimethylsiloxane macromer (molecular weight) in a reaction vessel equipped with an argon sparger, a temperature probe, a reflux cooler and an inlet port 30,000) is added at a reaction ratio of 10.5: 61: 3.5: 25 and toluene or isopropanol is added to bring the final monomer concentration to 20% by weight. The mixture is stirred and heated to 60 ° C. with a water bath while sparging argon for 1 hour. Azobisisobutyronitrile as an initiator is added to the mixture in an amount of 0.25% by weight of the monomer weight when toluene is the solvent and 0.125% by weight of the monomer weight when the isopropanol is the solvent. After sparging with argon, the reaction temperature was maintained at 60 ° C. for 6 hours, and then the solvent was removed in the same manner as in Polymer 2.

Carrier

In addition, the compositions of the present invention comprise a carrier or carrier mixture suitable for application to the hair. The phrase "suitable for application to hair" mentioned above means that the carrier does not damage the aesthetics of the hair, does not adversely affect, and does not irritate the skin. The carrier comprises a solvent and a vehicle component conventionally used in other carriers or hair care compositions, with about 0.5% to 99.5%, preferably about 5.0% to 99.5%, most preferably in the composition of the total hair composition Is present in about 10.0% to 90.0%.

The solvent as the carrier is selected by the copolymer used, regardless of whether the formulated hair composition remains in the hair after use, such as hair spray, mousse, tonic, or the like, or is cleaned, such as shampoo, conditioner, and the like. The solvent must be able to dissolve or disperse the specific silicone copolymer to be used, and in particular, the nature and proportion of monomer B in the copolymer primarily determines the polarity and solubility of the solvent. In addition, silicone copolymers can be designed to formulate a wide variety of solvents by combining the appropriate monomers. Suitable solvents for use in the present invention include water, lower alcohols (ethanol, isopropanol, etc.), hydroalcoholic mixtures, hydrocarbons (isobutane, hexane, decene, etc.), acetone, halogenated hydrocarbons (freons, etc.), hydrocarbon esters (ethyl acetate, Dibutyl phthalate, etc.), volatile silicone derivatives, siloxanes (phenyl pentamethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethyl Cyclopentasiloxane, and the like) and mixtures thereof. Preferred solvents include water, ethanol, volatile silicone derivatives and mixtures thereof. The solvents used may or may not be mixed with each other.

If the hair care composition is a conditioner composition, it may comprise a gel vehicle material as a carrier. The vehicle may incorporate one or more lipid vehicles that are substantially water insoluble and may contain hydrophobic and hydrophilic moieties. Lipid vehicle materials include acids, acid derivatives, alcohols, esters, ethers, ketones, and amides derived naturally or synthetically from about 12 to 22 carbon atoms, preferably about 16 to 18 carbon atoms, and include fatty alcohols and Fatty esters are preferred, and fatty alcohols are more preferred.

Preferred vehicles for use in the hair compositions of the present invention are hydrophobically modified hydroxyethyl cellulose materials and thickeners (such as locust bean gum), especially surfactants, quaternary ammonium compounds (such as ditallow dimethyl ammonium chloride) and / or Mixtures with chelating agents (EDTA, etc.).

Other carriers suitable for use in the present invention are used in the form of tonics, mousses, gels and hair sprays, etc., tonics, gels and non-aerosol hair sprays use solvents such as water or alcohols, mousse and aerosol hair Sprays in addition use propellants such as trichlorofluoromethane, dichlorodifluoromethane, dimethylether, propane, n-butane or isobutane. The amount of propellant can be adjusted as needed, but is generally about 3% to 30% of the total composition for mousse and about 15% to 50% of the total composition for aerosol hair spray.

Tonic or hair spray products of low viscosity may be added with an emulsifier to homogeneously disperse the silicone copolymer in solution as needed, and suitable emulsifiers include nonionic, cationic, anionic surfactants or mixtures thereof. Such emulsifiers are present in amounts of about 0.25% to 7.5% of the total composition.

Arbitrary additives

The hair protection composition of the present invention further comprises optional additives in addition to the silicone-containing copolymer and carrier described above. The hair protection compositions of the present invention can be formulated in a variety of product forms, including mousse, gel, lotion, tonic, spray, shampoo and conditioner, with the additional ingredients required to formulate such products vary depending on the form of the product. In addition, substances commonly used in hair protection products may be added.

Representative of optional ingredients include surfactants used in particular in shampoos and conditioner compositions. Surfactants useful in the compositions of the present invention include anionic, nonionic, cationic, amphoteric surfactants. Synthetic anionic surfactants include alkyl and alkyl ether sulfates, especially in the case of shampoo compositions, wherein the ratio of the styling agent silicone-containing copolymer to the detergent surfactant is controlled so that the styling agent is not completely washed off by the detergent. In addition, the ratio of the silicone-containing copolymer and the surfactant is preferably 1: 3 to 1:35. When the ratio of the silicone-containing copolymer to the surfactant is less than 1: 3, the dispersion of the silicone-containing copolymer is not easy and phase stability is low. When the ratio exceeds 1:35, the silicone-containing copolymer remains in the head. It is washed off and removed completely without the desired physical properties.

In addition, the compositions of the present invention may include a variety of optional ingredients to provide additional benefits, such as preservatives, viscosity modifiers, pH adjusters, colorants, hair oxidizers, hair reducing agents, perfumes, polymeric plasticizers, and the like.

EXAMPLE

The following presents preferred examples and comparative examples to aid in understanding the invention. However, the following examples are merely provided to more easily understand the present invention, and the present invention is not limited to the following examples.

Example 1-6

Xanthan gum was dissolved in water in a conventional mixing manner, and the remaining main mixing components shown in Table 1 were added thereto, and the main mixture was stirred at a temperature of 55 ° C. at a speed of 200 rpm for 3 hours. The shampoo composition was prepared by continuously adding the styling agent with stirring the mixture for about 10 minutes and by cooling the batch to room temperature while stirring the mixture. Each additive component was mixed in the content as shown in Table 1. Since the particle size varies, the styling agent can be added at different times using a high speed disperser, general agitation, or both. Phase stability was observed immediately after preparation, and the results are shown in Table 1. From the results, it can be seen that phase separation occurs only for the composition of Example 4 to which the styling agent is added 15%.

TABLE 1

Silicone Copolymer 1: Acrylic Acid / Vinyl Pyrrolidone / Polydimethylsiloxane Macromer (Molecular Weight 8,000) (10:70:20) Copolymer

Silicone Copolymer 2: N, N-dimethylacrylamide / isobutyl methacrylate / polydimethylsiloxane macromer (molecular weight 20,000) (20:60:20) copolymer

Silicone Copolymer 3: N, N-dimethylacrylamide / vinyl pyrrolidone / 2-ethylhexyl methacrylate / polydimethylsiloxane macromer (molecular weight 30,000) (10.5: 61: 3.5: 25) copolymer

Kathon CG: Preservative (Rohm & Haas)

Comparative Example 1

Acrylic acid / vinyl pyrrolidone / polydimethylsiloxane monomethacrylate (10:70 :) using polydimethylsiloxane monomethacrylate comprising one vinyl group as described in US Patent Application No. 07 / 505,755 instead of silicone copolymer 1. 20) A shampoo composition having the same composition as in Example 3 was prepared except that the copolymer was used.

Comparative Example 2

A shampoo composition having the same composition as in Example 3 was prepared except that vinyl pyrrolidone / vinyl acetate (Luviskol 64w, BASF) was used instead of silicone copolymer 1 as a styling agent.

The shampoo compositions of Examples and Comparative Examples were used to evaluate curl retention, measure friction coefficients, and evaluate hair feel and strength.

Curl retention test

Experiments were conducted to evaluate the degree of curl retention that the hair resists to external forces while maintaining some form. A hair tress having a length of 20 cm and a weight of 0.8 g was treated with 10% sodium lauryl sulfate solution for 3 minutes, washed with lukewarm water for 30 seconds, and dried. This hair tress was treated with the solution of 10% shampoo composition of Examples 1, 2, 3, 5, 6 (except Example 4 in which phase separation occurred) and Comparative Examples 1, 2, and then washed with lukewarm water flowing for 30 seconds. Drained off. The hair tress was pressed in a jig having a length of 15 cm and a depth of 1 cm and stored in a constant temperature and humidity chamber (temperature: 24 ° C., humidity: 47% RH) to make curls.

The curled hair tress was measured by 20% elongation on an instron, and the change rate was calculated by the difference between the initial daily value and the daily value after 15 repeated experiments. The results obtained therefrom are shown in Table 2 and FIG.

Friction test

The coefficient of friction of the hair to which the product was applied was measured to determine the conditioning effect of the shampoo composition. After treating the hair tress with 5% sodium lauryl sulfate solution for 5 minutes, the coefficient of friction was measured in the wet and dry state, respectively. However, in the wet state, the friction coefficient was measured at the contact surface between the silicone rubber and the hair under 500 g load, and in the dry state, the friction coefficient was measured at the contact surface between the isonitrile-butadiene rubber and the hair under 100 g load. The hair tress was treated with the 4% shampoo composition solution of Examples 1, 2, 3, 5, 6 (except Example 4 in which phase separation occurred) and Comparative Examples 1, 2, and then wet and dried, respectively. The coefficient of friction was measured. In wet and dry conditions, the conditioning effect was evaluated using the difference between the coefficient of friction of the hair treated with the shampoo composition and that of the hair treated with the sodium lauryl sulfate solution, and the results are shown in Table 2. .

Relative evaluation of hair feel and strength

Each of the shampoo compositions of Examples 1, 2, 3, 5, 6 (except Example 4 in which phase separation occurred) and Comparative Examples 1, 2 was applied to 10 female hairs for relative evaluation of hair texture and strength. . Experienced hair evaluator used each shampoo composition to wind and dry the hair, and then evaluated the hair texture and strength for the following items, and the evaluation result was determined to be 90% reliability.

1. Feel for dry hair

A: It's soft.

B: It is normal.

C: Stiff

2. strength felt from hair

A: Great

B: Normal

C: small

The results are shown in Table 2.

TABLE 2

Curl holding test, friction coefficient measurement and relative evaluation of hair feel and force

In Table 2, comparing the hair compositions of Examples 1, 2 and 3, it can be seen that the composition of Example 3 is the most desirable because it shows a low rate of change in the curl holding test, and a high value in the coefficient of friction. According to the mixing ratio of the cleaning agent in the styling agent and the main mixture composition, it was estimated that the more the cleaning agent is mixed, the more the styling agent is washed away without remaining in the hair and thus the curl holding force and the coefficient of friction decrease. From this, it was found that the optimum result was obtained when the mixing ratio of the styling agent and the cleaning agent was 10:35 as in Example 3. In addition, since the initial working value and the rate of change were both excellent in the case of Example 3 as a result of the curl retention test of Example 3 and Comparative Example 1, Comparative Example 1, which is a pendant bond using monomer C having one vinyl group It can be seen that the composition of Example 3 crosslinked using the monomer Twin C as in the present invention has a stronger setting force. In terms of the coefficient of friction, the compositions of Example 3 and Comparative Example 1 showed almost the same results, and it was found that the two compositions were equivalent in terms of conditioning effect.

Comparing the composition of Example 3 with Comparative Example 2, it can be seen that the composition of Example 3 is excellent in both the curl holding force and the friction coefficient, and also shows excellent results in the relative evaluation of the hair feel and the hair force. . Therefore, it can be seen that the silicone-containing copolymer of the present invention is superior in terms of hair strength (curl retention) and hair feel (friction coefficient) than previously known setting formulations.

The hair application composition of the present invention has almost the same rigidity as the material having a general setting function, the hair does not become sticky or stiff after application, does not adversely affect the hair properties after drying, and combing is easy, and the styling composition is again Can be restyled multiple times without application, resulting in excellent hair conditioning and style retention properties.

1 is a graph showing the results of the curl retention test of the shampoo composition according to an embodiment of the present invention and the shampoo composition according to the prior art.

Claims (6)

(a) 0 to 80% by weight of at least one vinyl monomer A polymerizable with (i) free radicals, (ii) at least one reinforcing monomer copolymerizable with monomer A, monomer B selected from the group consisting of a polar monomer and a macromer, 0 to 80% by weight, and  (iii) a molecular weight of 1,000 to 50,000, comprising 0.01 to 50% by weight of one monomer Twin C selected from the group consisting of Formulas 2,3 and 4,  Silicone-containing copolymers with a vinyl polymeric backbone grafted with divalent siloxane polymeric moieties of 10,000 to 1,000,000 molecular weight, 0.01 to 30.0 weight percent, and (b) suitable carriers for application to hair, 0.5 to 99.5 weight percent Hair application composition comprising: [Formula 2] [Formula 3] X-Si (R ² ) ₂ ―Z _m X [Formula 4] (In the formula 2, 3 and 4 m is 1, 2, or 3, p is 0 or 1, q is an integer from 0 to 2, R ² is lower alkyl, aryl, alkoxy, alkylamino and hydroxyl having 1 to 5 carbon atoms One selected from the group consisting of groups, X is Wherein R ³ is hydrogen or a —COOH group, R ⁴ is one selected from the group consisting of hydrogen, methyl and —CH ₂ COOH, Z is Where r is an integer from 5 to 700. 2. The hair application composition of claim 1, wherein the silicone-containing copolymer comprises 10 to 70 wt% Monosaccharide A, 7.5 to 80 wt% monomer B and 2 to 25 wt% monomer Twin C. The process of claim 1 wherein monomer A is vinyl chloride, vinylidene chloride, vinyl propionate, α-methylstyrene, tert-butylstyrene, butadiene, cyclohexadiene, ethylene, propylene, vinyl toluene, acrylonitrile, A hair application composition selected from the group consisting of oxy ethyl acrylate, acrylic acid or methacrylic acid esters of alcohols having from about 1 to 18 carbon atoms, styrene, polystyrene macromers, vinyl acetate, and mixtures thereof. The monomer of claim 1 wherein monomer B is tert-butyl acrylamide, maleic acid, maleic anhydride and its half esters, crotonic acid, itaconic acid, acrylamide, acrylate alcohol, hydroxyethyl methacrylate, acrylic acid, meta Krylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethyl aminoethyl methacrylate, methacrylamide, diallyldimethyl ammonium chloride, vinyl pyrrolidone, vinyl ether, maleimide, vinyl pyridine , Vinyl imidazole, polar vinyl heterocycle, styrene sulfonate, allyl alcohol, vinyl alcohol, vinyl caprolactam, and mixtures thereof prepared by hydrolyzing vinyl acetate after polymerization. The hair application composition of claim 1, wherein the hair application composition is in the form of a shampoo, conditioner, rinse, hair spray, lotion, mousse, hair tonic and gel. The hair application composition of claim 1, further comprising a surfactant when the hair application composition is a shampoo composition, wherein the weight ratio of the silicone-containing copolymer to the surfactant is 1: 3 to 1:35.