KR100505468B1 - Hairspray composition and pump typed hairspray spray system using the same - Google Patents

Abstract

The present invention relates to a hairspray composition and a pump type hairspray spraying system using the same, wherein the hairspray composition of the present invention comprises 0.0001 to 20% by weight of an ultraviolet absorbing monomer unit and 50 to 95% by weight of a (meth) acrylate monomer unit. 1 to 20% by weight of a copolymer comprising 2 to 14% by weight of a monomer unit containing a carboxyl group and 0.1 to 30% by weight of a monomer unit containing a polysiloxane group; 0.01 to 90% by weight of water; And 0.01 to 90% by weight of propylene glycol. The hairspray composition according to the present invention minimizes side effects due to UV exposure of the hair and can give a set holding power to the hair for a long time, and does not cause skinning, so it is applied to a pump type hairspray injection system. It is possible to prevent clogging of the exit outlet orifice so that uniform spraying is possible.

Description

Hairspray composition and pump typed hairspray spray system using the same}

The present invention relates to a hairspray composition and a pump type hairspray injection system using the same, and more particularly, to minimize the side effects of UV exposure of the hair and to give the set holding power to the hair for a long time, skinning ( The present invention relates to a hairspray composition capable of preventing the outlet orifice from being clogged when applied to a pump type hairspray injection system, and a pump type hairspray injection system using the same.

As ultraviolet ray transmission amount due to ozone layer destruction increases, there is a growing interest in the effect of ultraviolet rays on the skin. Dermatologically, the ultraviolet rays contained in the sun are classified into 400-320 nm long wavelength ultraviolet rays (UV-A), 320-290 nm medium wavelength ultraviolet rays (UV-B), and 290 nm or shorter ultraviolet rays (UV-C).

Among these, short-wave ultraviolet (UV-C) is absorbed by the ozone layer in the atmosphere and hardly reaches the surface, but medium-wave ultraviolet (UV-B) and long-wave ultraviolet (UV-A) cause various skin disorders in the human body. It is known to cause. For example, long-wave ultraviolet (UV-A) not only causes skin darkening, but its energy reaches the dermis and affects the carbon fibers in the blood vessel walls or connective tissue. In addition, when the skin is excessively exposed to medium-wave ultraviolet (UV-B) and long-wave ultraviolet (UV-A), red spots or blisters occur on the skin, promote aging of the skin, and cause wrinkles and freckles. Known.

In particular, ultraviolet rays adversely affect hair. In other words, ultraviolet rays oxidize and decompose melanin inside the hair to redden the hair and cause the strength of the hair to fall. As it is found that ultraviolet rays adversely affect human skin and hair, research is actively conducted to impart a function to protect hair from ultraviolet rays even in hairsprays that facilitate hair preparation and styling. have.

However, satisfactory results are not obtained when conventional sunscreens or absorbers are added to the hairspray composition. That is, a sunscreen such as titanium oxide particles exhibits the effect only when they have an appropriate particle size, but it is not only difficult to control the particle size but also difficult to uniformly disperse the particles. In addition, organic ultraviolet absorbers such as 4-amino benzoic acid, cinnamic acid, benzophenone, and the like have low molecular weights and have disadvantages such as volatility, transferability, and extractability.

In addition, due to the nature of the pump type hairspray injection system to which the hairspray composition is applied, it is necessary to prevent the outlet orifice from clogging due to skinning of the hairspray composition.

Therefore, the technical problem to be achieved by the present invention is to solve the above problems to minimize the side effects of ultraviolet light exposure of the hair and to give the set holding power to the hair for a long time, as well as skinning (skinning) does not occur pump type It is to provide a hairspray composition which can prevent the outlet orifice from being blocked when applied to the hairspray injection system of the present invention.

In addition, another technical problem to be achieved by the present invention is to provide a pump type hairspray injection system using the hairspray composition.

In order to achieve the above technical problem, the present invention is 0.0001 to 20% by weight of the ultraviolet absorbing monomer unit represented by the following formula (1), 50 to 95% by weight of the (meth) acrylate-based monomer unit, monomer units 2 to 14 containing a carboxyl group 1 to 20% by weight of a copolymer or a neutralizer thereof composed of 0.1 to 30% by weight of a monomer unit containing% by weight and a polysiloxane group; 0.01 to 90% by weight of water; And propylene glycol 0.01 to 90% by weight; provides a hairspray composition comprising a.

In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group having 1 to 3 carbon atoms.

The ultraviolet absorbent monomer unit of the copolymer according to the present invention has a strong absorption capacity against the long-wavelength ultraviolet (UV-A) and the medium-wave ultraviolet (UV-B) problem is excellent in hair protection against ultraviolet rays. In addition, unlike conventional UV absorbers, since the polymer is a copolymer copolymerized with other monomers, there is no fear of deterioration of aging stability due to evaporation or extraction. As such an ultraviolet absorbing monomer unit, hydroxy acryloxy ethylphenyl benzotriazole, hydroxy methacryloxy ethylphenyl benzotriazole, hydroxy methacryloxy propylphenyl benzotriazole, etc. can be used individually or in copolymerization. The content of the UV absorbing monomer unit is a range in which the protective effect of UV invasion of the hair coated with the copolymer, the flexibility and the adhesion of the hair are good, and 0.0001 to 20% by weight based on the total weight of the copolymer is more preferable. Is 0.5 to 10% by weight.

Examples of the (meth) acrylate monomer unit of the copolymer according to the present invention include methyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and the like. It may be used alone or in copolymerization. The (meth) acrylate monomer unit controls the film strength of the copolymer applied to the hair, and serves to maintain the initial physical properties. The content of the (meth) acrylate monomer unit is 50% based on the total weight of the copolymer, considering that the hair does not become entangled due to the softening of the film applied to the hair when the hair spray is used. ~ 95% by weight is appropriate.

As a monomer unit containing a carboxyl group of the copolymer according to the present invention, acrylic acid, methacrylic acid, itaconic acid, or the like may be used alone or copolymerized. Such a monomer unit containing a carboxyl group may impart a hydrophilic property to the copolymer to provide hair. It acts to improve the water solubility in the manufacture of the spray, and makes it easy to remove the hairspray from the hair by facilitating trituration when washing the hair. When the content of the monomer unit containing a carboxyl group maintains good hair cleanability and water solubility and maintains a high setting force even when absorbing moisture in the air, considering the range of minimizing stickiness causing hair entanglement, Suitable 2 to 14% by weight based on the total weight of the copolymer, preferably 5 to 10% by weight.

Monomer units containing a polysiloxane group of the copolymer according to the present invention include polydimethylsiloxane, α-butyldimethylsiloxy-ω- (δ-methacryloxypropyl), α-butyldimethylsiloxy-ω- (δ-di Methacrylicoxypropyl) and the like can be used alone or in copolymerization. Such a monomer unit containing a polysiloxane group gives lubricity and flexibility to the copolymer film applied to the hair and significantly reduces stickiness. The content of the monomer unit containing a polysiloxane group is appropriately 0.1 to 30% by weight based on the total weight of the copolymer, considering that it is expensive compared to other monomers and that beads are formed on the hair when used in excess.

The copolymer according to the present invention described above can be prepared by the following solution polymerization method.

First, the ultraviolet absorbing monomer which forms a copolymer, the (meth) acrylate type monomer, the monomer containing a carboxyl group, and the monomer containing a polysiloxane group are dissolved in a solvent. As a solvent, it is preferable to use C1-C2 alcohols, such as methanol and ethanol which are water-soluble organic solvents, individually or in mixture. The reaction initiator is added thereto and heated and stirred under a nitrogen atmosphere to polymerize. The reaction initiator to be added is a hydrogen peroxide, t-butylperate, which is easily soluble in the vinyl monomers and the solvent constituting the copolymer and excellent in radical generation ability. It is preferable to use peroxides such as oxides or benzoyl peroxides, and azo compounds such as azobisisobutylonitrile and azobisdimethylvaleronitrile can also be used. It is preferable to adjust the addition amount of a reaction initiator so that the weight average molecular weight of the copolymer obtained may be about 5,000-100,000. In addition, the reaction temperature is based on the reflux temperature of the solvent used, the reaction time is preferably about 4 to 6 hours so that the conversion of the monomer constituting the copolymer is 99.8% or more.

The copolymer thus prepared is preferably neutralized in consideration of cleanliness, stickiness, and hair styling retention after application to the hair. Neutralization is carried out by dissolving a water-soluble organic basic neutralizing agent or inorganic basic neutralizing agent in an alcohol or the like to react with the copolymer. do. As the water-soluble organic basic neutralizing agent used at this time, for example, morpholine, monoethanolamine, diethanolamine, triethanolamine, monoisopropylamine, diisopropylamine, triisopropylamine, 2-amino-2-methyl- 1-propanol and the like, and alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and calcium hydroxide may be used as the water-soluble inorganic basic neutralizing agent. The content of the copolymer or its neutralizing agent is 1 to 20% by weight of the copolymer or its neutralizing agent based on the total weight of the composition. If the content is less than 1% by weight, the setting force may be lowered. When the film is formed on the hair, it may be thickly applied to cause agglomeration and flaking of the hair. More preferred content of the copolymer or its neutralizer is 2 to 8% by weight, based on the total weight of the composition.

The copolymer or its neutralizer is added to the hairspray composition with water and propylene glycol.

Application of the copolymer to ethanol, which is used as a conventional solvent for hairspray, results in a skinning phenomenon in which the copolymer solidifies at the interface of air contact. When the solidified hairspray composition is sprayed through the outlet orifice, there is a problem that the injection hole of the outlet orifice is clogged. According to the present invention, when water and propylene glycol are used in an appropriate amount, skinning can be prevented, so that uniform spraying is achieved. Not only is it possible, but the alcohol odor is drastically reduced, resulting in a subtle odor. The content of water and propylene glycol is 0.01 to 90% by weight, respectively, based on the total weight of the composition, and the preferred content is 1 to 40% by weight, respectively.

In addition, the hairspray compositions of the present invention are conventional hairspray additives such as setting polymers that can fix or style hair, additives that impart moisturizing and conditioning effects, neutralizers, pH adjusters, flavorings, hair protectants, colorants, and ethanol. It may further contain.

Such a hairspray composition according to the present invention can be applied to a conventional pump type hairspray spraying system in which the hairspray composition contained in the container is sprayed into the fine particles through the outlet orifice. In the pump type hairspray injection system, it is very important to properly select the nozzle diameter of the outlet orifice. If the nozzle diameter of the outlet orifice is not appropriate, the nozzle may be blocked due to the setting agent or the hair spray composition may not be sprayed and may flow down.

The pump type hairspray spraying system to which the hairspray composition of the present invention described above is applied prevents the blockage of the jetting port by the hairspray composition when the diameter of the jet port has an outlet orifice of 0.005 to 0.030 inch, preferably 0.010 to 0.020 inch. It is possible to form an excellent spray pattern while preventing. In particular, when the single injection amount is adjusted to 0.05 to 0.30g, more preferably 0.07 to 0.20g to form the injection particles in the most appropriate size.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Synthesis Example 1

131 g of anhydrous ethanol was added to a 2 L reaction vessel equipped with a thermometer, a nitrogen input tube, a reflux condenser and a stirrer, and then heated to 80 ° C. under a nitrogen atmosphere. Subsequently, 58 g of 0.3 wt% solution of benzoyl peroxide dissolved in ethanol was added to the reaction vessel at once, followed by 205.9 g of t-butyl acrylate, 20.3 g of t-butyl methacrylate, 29 g of acrylic acid, polydimethylsiloxane and α-butyl Over 3 hours into the reaction vessel through a dropwise addition of a monomer solution mixed sufficiently at a ratio of 34.8 g of dimethylsiloxy-ω- (δ-methacryloxypropyl) and 0.29 g of hydroxymethacryloxy ethylphenyl benzotriazole. The polymerization was carried out under reflux with continuous dropping. When the addition of the monomer mixed solution was completed, 116 g of 0.6 wt% solution of benzoyl peroxide dissolved in ethanol was continuously added to the reaction vessel over about 1 hour, followed by stirring at the same temperature for 1 hour. Then, in order to increase the conversion of the polymer, 58 g of a benzoyl peroxide 2% by weight solution dissolved in ethanol was added, and stirred at the same temperature for about 2 hours or more to prepare a copolymer. Subsequently, the internal temperature of the reaction vessel was cooled to about 40 ° C. or lower, and then 217 g of a 8.7 wt% potassium hydroxide solution dissolved in ethanol was added thereto, followed by sufficient stirring to neutralize the copolymer.

The average molecular weight of the neutralization copolymer obtained by Water Gel Gel Chromatography (GPC) using polystyrene as a standard was found to be about 70,000.

Synthesis Example 2

The amount of added monomer was 188.2 g of t-butyl acrylate, 20.3 g of t-butyl methacrylate, 37.7 g of acrylic acid, 34.8 g of polydimethylsiloxane and α-butyldimethylsiloxy-ω- (δ-methacryloxypropyl), and The reaction was carried out in the same manner as in Example 1, except for changing to 0.29 g of hydroxy methacryloxy ethylphenyl benzotriazole and adding 2-amino-2-methyl-1-propanol instead of potassium hydroxide as a neutralizing agent.

The average molecular weight of the obtained neutralized copolymer was found to be about 82,300.

Synthesis Example 3

The amount of monomer added was 187 g of t-butyl acrylate, 20.3 g of t-butyl methacrylate, 37.7 g of acrylic acid, 34.8 g of polydimethylsiloxane and α-butyldimethylsiloxy-ω- (δ-methacryloxypropyl) and hydroxy. The reaction was carried out in the same manner as in Example 1, except that 2-hydroxy-2-methyl-1-propanol was added instead of potassium hydroxide as a neutralizing agent, and changed to 1.45 g of oxy methacryloxy ethylphenyl benzotriazole.

The average molecular weight of the obtained neutralized copolymer was found to be about 85,400.

Synthesis Example 4

The amount of monomer charged was 148 g of t-butyl acrylate, 43.5 g of t-butyl methacrylate, 37.7 g of acrylic acid, 58 g of polydimethylsiloxane and α-butyldimethylsiloxy-ω- (δ-methacryloxypropyl) and hydroxy. The same procedure as in Example 1 was carried out except that the methacryloxy ethylphenyl benzotriazole was changed to 2.9 g.

The average molecular weight of the obtained neutralized copolymer was found to be about 73,000.

Synthesis Example 5

The amount of monomer charged was 145 g of t-butyl acrylate, 43.5 g of t-butyl methacrylate, 37.7 g of acrylic acid, 58 g of polydimethylsiloxane and α-butyldimethylsiloxy-ω- (δ-methacryloxypropyl) and hydroxy. The same procedure as in Example 1 was carried out except for changing to 5.8 g of methacryloxy ethylphenyl benzotriazole.

The average molecular weight of the obtained neutralized copolymer was found to be about 72,720.

Comparative Example 1

131 g of anhydrous ethanol was added to a 2 L reaction vessel equipped with a thermometer, a nitrogen input tube, a reflux condenser and a stirrer, and then heated to 80 ° C. under a nitrogen atmosphere. Subsequently, 58 g of 0.3 wt% solution of benzoyl peroxide dissolved in ethanol was added to the reaction vessel at once, and then a monomer solution sufficiently mixed in a ratio of 241 g of t-butyl acrylate, 20.3 g of t-butyl methacrylate and 29 g of acrylic acid was added. The polymerization was carried out under reflux while continuously dropping into the reaction vessel over about 3 hours through dropping. When the addition of the monomer mixed solution was completed, 116 g of 0.6 wt% solution of benzoyl peroxide dissolved in ethanol was continuously added to the reaction vessel over about 1 hour, followed by stirring at the same temperature for 1 hour. Then, in order to increase the conversion of the polymer, 58 g of a benzoyl peroxide 2% by weight solution dissolved in ethanol was added, and stirred at the same temperature for about 2 hours or more to prepare a copolymer. Subsequently, the internal temperature of the reaction vessel was cooled to about 40 ° C. or lower, and then 217 g of a 8.7 wt% potassium hydroxide solution dissolved in ethanol was added thereto, followed by sufficient stirring to neutralize the copolymer.

The average molecular weight of the neutralized copolymer obtained by Water Gel Gel Chromatography (GPC) using polystyrene as a standard was found to be about 65,700.

Comparative Example 2

The type and content of the added monomer were 148 g of t-butyl acrylate, 43.5 g of t-butyl methacrylate, 37.7 g of acrylic acid, and 58 g of polydimethylsiloxane and α-butyldimethylsiloxy-ω- (δ-methacryloxypropyl). A neutralization copolymer (average molecular weight about 72,720) was obtained and 2.9 g of 2- (2'-hydroxy-5'-methylphenyl) benzotriazole was blended in the same manner as in Comparative Example 1 except for the change. .

5 g of the polymers prepared according to Synthesis Examples 1 to 5 and Comparative Examples 1 to 2 and 95 g of ethanol were mixed and stirred, and the ultraviolet absorption intensity was evaluated using the US Hewlett Packard UV spectrometer as follows. The above-described compound was contained in 10 ml of quartz cells and the absorption intensity at 338 nm, which is the maximum wavelength, was measured. In addition, in order to evaluate the effect of sustaining light stabilization with time, the absorption intensity was measured immediately after the preparation of the formulation, after 24 hours, and after 72 hours.

Active ingredient of the combination Each monomer content in active ingredient A / B / C / D / E Neutralization degree (%) Average molecular weight (g / mol) UV absorption intensity Right after manufacturing After 24 hours After 72 hours Synthesis Example 1 71/7/10/12 / 0.1 80 70,000 0.476 0.464 0.458 Synthesis Example 2 64.9 / 7/13/15 / 0.1 70 82,300 0.478 0.461 0.442 Synthesis Example 3 64.5 / 7/13/15 / 0.5 80 85,400 1.673 1.665 1.651 Synthesis Example 4 51/15/13/20/1 80 73,000 2.344 2.341 2.338 Synthesis Example 5 50/15/13/20/2 80 72,720 2.588 2.581 2.575 Comparative Example 1 83/7/10/0/0 80 65,700 0.012 ND ND Comparative Example 2 51/15/13/20/1 80 68,000 2.366 2.094 1.875

In Table 1, A is t-butyl acrylate, B is t-butyl methacrylate, C is acrylic acid, D is polydimethylsiloxane and α-butyldimethylsiloxy-ω- (δ-methacryloxypropyl) , E represents hydroxy methacryloxy ethylphenyl benzotriazole in Synthesis Examples 1 to 5, and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole in Control Example 2.

Referring to Table 1, a copolymer (Synthesis Examples 1 to 5) composed of a UV absorbing monomer unit, a (meth) acrylate monomer unit, a monomer unit containing a carboxyl group, and a monomer unit containing a polysiloxane group according to the present invention are contained. It can be seen that the blend is excellent in the ability to absorb ultraviolet light and the effect of sustaining light stabilization.

On the other hand, the formulation of Comparative Example 1, which does not include the UV absorbing monomer unit, is particularly poor in UV absorption strength, and unlike the copolymer of the Synthetic Example, the formulation of Comparative Example 2, which is simply blended with a low molecular weight sunscreen, has a UV light over time. Absorption intensity can be significantly reduced.

Examples 1 to 9 and Comparative Examples 1 to 2

To prepare a hairspray composition according to the conventional hairspray manufacturing method according to the ingredients and contents shown in Table 2. The hairspray compositions according to the examples and comparative examples were evaluated for the setting force and the skinning phenomenon, and at the same time, the pump clogging test was carried out by applying to a pump type hairspray injection system having an outlet orifice having a predetermined nozzle diameter. It is shown in Table 2.

<Setting force evaluation>

A hairspray composition according to Examples and Comparative Examples was applied to 23 cm and 2 g of hair, and wound and dried on a spiral. Then, the hair without the spiral was left in a constant temperature and humidity room with a temperature of 25 ° C. and a relative humidity of 80%, and the hair length after 3 hours was measured, and the set retention force was calculated according to the following Curl retention formula. .

Curl Retention (%) = (L0-L2) / (L0-L1)

L0: Hair length before hair mousse treatment

L1: Length of hair before standing in constant temperature and humidity room

L2: Length after 3 hours left in constant temperature and humidity room

<Skinning phenomenon evaluation>

The hairspray composition was placed in a container without a cover, and then left for 1 day at room temperature to visually observe the skinning phenomenon appearing on the surface thereof and evaluated according to the following criteria.

(Evaluation standard)

No skinning phenomenon (very good): ◎

No skinning phenomenon (good): ○

Skinning occurs but is weak (usually): △

Skinning phenomenon (defect): ×

<Pump Clogging Test>

While spraying the hairspray composition at 50 ° C., it was sprayed for 10 seconds at a time over a few days through an outlet orifice having a nozzle diameter shown in Table 2 below, and then the spray condition was visually observed and evaluated according to the following criteria.

(Evaluation standard)

Uniform spray pattern maintenance (very good): ◎

Slightly irregular spray pattern Maintains uniform spray pattern (good): ○

Spray pattern is irregular shape or particle drop phenomenon (bad / clogging): △

Not sprayed (blocked): ×

In Table 2 above, the setting agent is a copolymer according to Synthesis Example 5.

Referring to Table 2, the hairspray according to the embodiment containing the appropriate amount of the copolymer of the setting agent 1, water and propylene glycol not only has excellent hair setting power, but also does not cause skinning, and has an appropriate nozzle diameter. It can be seen that uniform spraying is possible when applied to a pump-type hairspray spraying system with an outlet orifice having.

As such, the hairspray composition according to the present invention can minimize the side effects of ultraviolet light exposure of the hair and impart a set holding power to the hair for a long time, and skinning phenomenon does not occur. In addition, the application of such a hairspray composition to a pump type hairspray injector system having an outlet orifice having a nozzle diameter according to the present invention can maintain a uniform spray pattern without clogging the outlet orifice.

Claims (6)

Based on the total weight of the composition, 0.0001 to 20% by weight of an ultraviolet absorbing monomer unit represented by Formula 1; At least one (meth) acrylate monomer unit 50 to 95 selected from the group consisting of methyl (meth) acrylate, normal butyl (meth) acrylate, isobutyl (meth) acrylate and t-butyl (meth) acrylate weight%; 2 to 14% by weight of a monomer unit containing at least one carboxyl group selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid; And at least one polysiloxane selected from the group consisting of polydimethylsiloxane, α-butyldimethylsiloxy-ω- (δ-methacryloxypropyl) and α-butyldimethylsiloxy-ω- (δ-dimethacryloxypropyl) 0.1 to 30% by weight of a monomer unit containing groups; 1 to 20% by weight of a copolymer or a neutralizing agent thereof; 0.01 to 90% by weight of water; And 0.01 to 90% by weight of propylene glycol; hairspray composition, characterized in that it comprises; <Formula 1> In Formula 1, R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkyl group having 1 to 3 carbon atoms. delete delete delete A pump type hairspray spraying system for spraying a hairspray composition into fine particles through an outlet orifice, Claim 1 hairspray composition; A container containing the hairspray composition; And And an outlet orifice having a diameter of 0.005 to 0.030 inch in diameter of the jet port. 6. The pump type hairspray injection system according to claim 5, wherein the single injection amount of the hairspray composition through the outlet orifice is 0.05 to 0.30 g.