KR20150066684A - Polymer nano composite particles containing chemical sunscreen agents and the method for preparing thereof - Google Patents

Abstract

The present invention relates to a polymeric nanocomposite particle containing a chemical sunscreen agent and a method for producing the same, and more particularly, to a nanocomposite particle having spherical polymer nanoparticles in which a chemical ultraviolet screening agent is bonded to the inner surface of a spherical polymeric nanoparticle, But also has a particle size of 10 to 800 nm, which is excellent in feeling of use when applied to cosmetics and can remarkably improve ultraviolet shielding performance, and a method for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymeric nanocomposite particle containing a chemical sunscreen agent and a method for producing the same. [0002]

The present invention relates to a polymeric nanocomposite particle containing a chemical sunscreen agent and a method for producing the same, and more particularly, to a nanocomposite particle having spherical polymer nanoparticles in which a chemical ultraviolet screening agent is bonded to the inner surface of a spherical polymer nanoparticle, The present invention relates to a polymer nanocomposite particle having a size of 10 to 800 nm which is very excellent in feeling of use when applied to cosmetics and can remarkably improve ultraviolet shielding performance, and a method for producing the same.

Recently, as the ultraviolet ray irradiation amount of the surface due to destruction of the ozone layer is increased, the market of products which are mainly used for ultraviolet ray blocking is growing every year.

Most organic sunscreens can cause physiological damage to the human body when used in amounts that are necessary to effectively block harmful ultraviolet light. Damage to the human body, specifically skin troubles, is caused by skin penetration of sunscreen agents.

In addition, the chemical sunscreen agent has poor stability against heat and light, has poor solubility in solvents, and has a limited use method and bad feeling. In order to overcome these problems, the organic UV blocking agent may be encapsulated in silicone resin or glass to be used as a core-shell type. However, since the shell is broken by a weak impact, there is a danger that the core material may come into contact with the skin to a great extent, And it is difficult to adjust the size of the capsule because it is manufactured in a core-shell form.

In order to solve the above problems, the present applicant filed and filed a Korean Patent Application No. 10-2007-0083469 filed for application to a polymer composite particle for a cosmetic composition containing a UV-blocking agent and a method for producing the same, but since the size of the polymer composite particle is in the form of micro- When applied to cosmetics, there is still a demand for improvement in feeling.

Accordingly, it is required to develop a composite particle having excellent feeling in use when applied to cosmetics, while being able to use the ultraviolet screening agent stably and efficiently.

The present invention relates to a cosmetic composition which combines a chemical ultraviolet screening agent, which is highly restricted in use, with an inner surface of a nano-sized spherical polymer material to minimize irritation to the skin, and can efficiently and stably use the cosmetic composition. And has excellent ultraviolet blocking effect, and a process for producing the same.

It is another object of the present invention to provide a cosmetic composition for protecting ultraviolet rays containing polymer nanocomposite particles containing the chemical sunscreen agent as an active ingredient.

In order to solve the above problem,

a) dissolving and dispersing a chemical sunscreen agent in a radical polymerizable monomer and a polyfunctional crosslinking monomer, and adding an initiator to prepare a dispersion;

b) emulsifying the dispersion containing the chemical sunscreen agent in a solvent in the presence of a dispersion stabilizer to form droplets;

c) homogenizing the droplets using a high pressure homogenizer;

d) polymerizing the homogenized droplets to prepare polymer nanocomposite particles; And

e) washing and drying the polymer composite particles prepared above

The present invention also provides a method for producing a polymer nanocomposite particle.

Also,

a) a polymer particle having a particle size of 10 to 800 nm in which a radically polymerizable monomer and a multi-functional crosslinking monomer are polymerized; And

and b) a polymeric nanocomposite particle having a chemical ultraviolet blocking agent bonded to the inner surface of the polymer particle.

The present invention also provides a cosmetic composition for protecting against UV rays, which comprises polymer nanocomposite particles containing a chemical sunscreen agent as an active ingredient.

The polymer nanocomposite particle containing the chemical sunscreen agent of the present invention binds a chemical ultraviolet screening agent, which is highly restricted in use, to the inner surface of a nano-sized spherical polymer material to minimize irritation to the skin and to use it effectively and stably In particular, when applied to cosmetics, the feeling of use is remarkably improved and the ultraviolet ray shielding effect is excellent.

The method for producing the polymer nanocomposite particle of the present invention comprises

a) dissolving and dispersing a chemical sunscreen agent in a radical polymerizable monomer and a polyfunctional crosslinking monomer, and adding an initiator to prepare a dispersion;

b) emulsifying the dispersion containing the ultraviolet screening agent in a solvent in the presence of a dispersion stabilizer to form droplets;

c) homogenizing the droplets using a high pressure homogenizer;

d) polymerizing the homogenized droplets to prepare polymer nanocomposite particles; And

e) washing and drying the polymer nanocomposite particles prepared above.

The chemical ultraviolet screening agent in step a) of the present invention is preferably a chemical ultraviolet screening agent that blocks ultraviolet rays through absorption, and is preferably an organic ultraviolet screening agent. Specific examples thereof include p-aminobenzoic acid (PABA) derivatives, cinnamate derivatives, salicylic acid derivatives, benzophenones, dibenzole methane, and anthranilates. They may be used alone or in combination of two or more. The ultraviolet screening agent is preferably contained in an amount of 0.1 to 200 parts by weight based on 100 parts by weight of the radical polymerizable monomer and the multifunctional crosslinking monomer.

The radically polymerizable monomer of the present invention can be copolymerized with a vinyl-based crosslinking monomer, and there is no particular limitation. Specific examples of the radical polymerizable monomer include aromatic vinyl compounds such as styrene, methylstyrene, ethylstyrene, fluorostyrene, chlorostyrene, and vinyltoluene; Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, stearyl Acrylic vinyl monomers such as methyl acrylate, ethyl acrylate, ethyl acrylate, and the like; (Meth) acrylonitrile, and the like. These monomers may be used singly or in combination of two or more.

The multifunctional crosslinking monomer is used for crosslinking the particles, and a multifunctional vinyl-based crosslinking monomer capable of copolymerizing with the radical polymerization monomers is used. Specific examples thereof include divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol dimethacrylate, trimethylene propane trimethacrylate, 1,3-butanediol methacrylate, 1,6- Hexanediol dimethacrylate, allyl (meth) acrylate, and tri (meth) acrylate. These may be used singly or in combination of two or more.

Preferably, the content ratio of the radical polymerizable monomer to the multifunctional crosslinking monomer is 5 to 95 parts by weight: 95 to 5 parts by weight, more preferably 30 to 70 parts by weight: 70 to 30 parts by weight. When the content of the polyfunctional crosslinking monomer is less than 5 parts by weight, the solvent resistance, heat resistance and mechanical properties of the produced particles are deteriorated. When the content of the polyfunctional crosslinking monomer is less than 5 parts by weight, have.

In the present invention, a commonly used method can be used for the dissolution and dispersion, and the initiator to be added can be used without any particular limitation as long as it can form a free radical. Specific examples include peroxide-based ones such as benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, and t-butyl hydroperoxide; Azo compounds such as 2,2'-azobisisobutylonitrile, 2,2'-azobis-2,4-dimethylvaleronitrile and 2,2'-azobis-2-methylisobutyronitrile, or And mixtures thereof. The initiator is preferably used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the radical polymerizable monomer and the polyfunctional crosslinking monomer. Within the above range, it is easy to increase the yield, to suppress the heat generation in the polymerization process, and to control the particle size.

 In the step b), the dispersion prepared in the step a) is emulsified in a solvent in the presence of a dispersion stabilizer to form droplets. The droplet formation can be performed by a commonly used method.

The dispersion stabilizer is used to prevent aggregation and precipitation of particles formed in the polymerization reaction, and specific examples thereof include cellulose derivatives such as methyl cellulose, ethyl cellulose and hydroxypropyl cellulose; Polyvinyl alcohol, polyvinyl methyl ether, polyacrylic acid, polyvinyl acetate or copolymers of polyvinylpyrrolidone and vinyl acetate; Colloidal silica and the like. The dispersion stabilizer is preferably contained in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the sum of the radical polymerizable monomer and the polyfunctional crosslinking monomer. If the concentration is less than 0.1 part by weight, there is a problem of flocculation. If the concentration is more than 20 parts by weight, a dispersion stabilizer may be gelated and a side reaction may occur.

As the solvent used in the above emulsification, ion-exchanged water, distilled water, alcohol, ether alcohol and the like may be used, or they may be used alone or in combination of two or more.

In the step c), the droplet is homogenized using a high-pressure homogenizer. In the present invention, the homogenization is preferably performed at a pressure of 500 to 2000 bar, preferably 800 to 1500 bar, and a nozzle diameter of 0.1 to 10 μm, preferably 1 to 5 μm. When the particle diameter is within the above range, the particle strength of the polymer nanocomposite particle to be polymerized is improved, so that the particle can be broken and the chemical ultraviolet blocking agent can be prevented from flowing out to the outside. As a concrete example, it is preferable to use NS 3037 of GEA Niro Soavi, the high-pressure homogenizer.

In the present invention, the polymerization in the step d) can be carried out by a polymerization method commonly used in the art. Specific examples thereof include suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization and the like, and suspension polymerization is particularly preferred in the present invention. In the polymerization, the polymerization is preferably carried out at 50 to 90 ° C for 5 to 50 hours. This is because a high conversion rate can be obtained. At this time, when the stirring speed is too high in the polymerization reaction, it may be preferable to maintain an appropriate stirring speed because aggregation may occur or a particle size may be changed to cause problems in size control.

In the present invention, the homogenized liquid droplets are polymerized by the high pressure homogenizer to polymerize the polymer nanocomposite particles having a particle size of 10-800 nm.

In step e), the polymer nanocomposite particles prepared in step d) are washed and dried.

The washing is carried out in order to reduce the amount of unreacted monomers present in the particles after filtration of the synthesized particles and to remove impurities such as initiators remaining after the polymerization reaction to prevent discoloration due to impurities even when the temperature during drying is raised , Polyhydric alcohols (ethylene glycol, propylene glycol, glycerin, etc.), aqueous solutions thereof, water, and the like can be used. Preferably, washing is carried out using ethanol, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol or octyl alcohol. At this time, the aqueous solution is preferably used in an amount of 1 to 30 wt% of the washing solution, and when used in the range, the removal efficiency of impurities can be increased.

It is preferable that the drying is performed in a vacuum state at a temperature lower than the glass transition temperature in consideration of the glass transition temperature of the particles after the removal of the impurities and the washing step.

The present invention also provides a polymer nanocomposite particle prepared by the above process for producing a polymer nanocomposite particle, wherein the polymer nanocomposite particle according to the present invention is characterized in that: (a) the particle size of the polymerized particle of the radically polymerizable monomer and the multi- Polymer particles of 10 to 800 nm; And b) a chemical ultraviolet screening agent is bound to the inner surface of the polymer particle.

The polymer nanocomposite particles according to the present invention have a particle size of 10 to 800 nm and are excellent in feeling of use when applied to a cosmetic composition and excellent in ultraviolet ray shielding effect and are excellent in that the polymer particles are not broken more than other sizes, There is an advantage that the phenomenon of leakage can be remarkably reduced.

The present invention also provides a cosmetic composition for protecting ultraviolet rays, which comprises polymer nanocomposite particles containing the ultraviolet screening agent as an active ingredient.

The cosmetic composition can be used by adding the polymer nanocomposite particles containing the ultraviolet screening agent to various formulations of the cosmetic composition, and preferably contains 0.01 to 30% by weight based on the total weight of the composition. If the content is less than 0.01% by weight, there is a problem that the ultraviolet ray shielding effect is insufficient. If the content is more than 30% by weight, problems may arise.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example 1]

A separable reactor equipped with a stirrer was charged with 13 parts by weight of methyl methacrylate as a radical polymerizable monomer, 1.3 parts by weight of ethylene glycol dimethacrylate as a multifunctional crosslinking monomer, 100 parts by weight of 2,2'-azo 0.2 part by weight of bis-2,4-dimethylvaleronitrile, 4.5 parts by weight of butylmethoxydibenzoylmethane as an ultraviolet blocking agent, 0.3 part by weight of polyvinyl alcohol as a dispersion stabilizer and 80.7 parts by weight of ion exchange water as a solvent were added, And emulsified at 8000 rpm for 10 minutes. The emulsified droplets were homogenized with a high pressure homogenizer at a pressure of 1000 bar and a nozzle size of 2 μm using NS 3037 from GEA Niro Soavi.

The homogenized liquid droplets were transferred to the reactor and the temperature was elevated to initiate polymerization at 60 ° C for 20 hours. The resultant polydisperse polymer particles were dehydrated using a vacuum filter, washed with ethanol several times, and dried in vacuo to obtain nanocomposite particles having a final particle size of 10-800 nm.

[Example 2]

The procedure of Example 1 was repeated, except that the pressure of the high-pressure homogenizer was set at 800 bar and the particle size of the nozzle was set at 1 μm.

[Example 3]

The procedure of Example 1 was repeated, except that the pressure of the high-pressure homogenizer was changed to 1500 bar and the particle size of the nozzle was changed to 3 μm.

[Example 4]

The procedure of Example 1 was repeated, except that 6.5 parts by weight of octylmethoxycinnamate was used instead of butylmethoxydibenzoylmethane as an ultraviolet screening agent in Example 1.

[Example 5]

The procedure of Example 2 was repeated, except that 6.5 parts by weight of octylmethoxycinnamate was used instead of butylmethoxydibenzoylmethane as an ultraviolet screening agent.

[Example 6]

The procedure of Example 1 was repeated, except that 6.5 parts by weight of octylmethoxycinnamate was used instead of butylmethoxydibenzoylmethane as an ultraviolet screening agent in Example 3.

[Comparative Example 1]

The procedure of Example 1 was repeated except that the high-pressure homogenizer was not used in Example 1. The particle size of the prepared polymer composite particles was 4 탆.

[Comparative Example 2]

The procedure of Example 4 was repeated except that the high-pressure homogenizer was not used in Example 1. The particle size of the prepared polymer composite particles was 5 탆.

[Test Example 1] Characteristic and ultraviolet blocking test

Formulation Examples 1 to 6 and Comparative Example 1

To confirm the ultraviolet blocking ability of the polymer composite particles prepared in Examples 1 to 6, UV-blocking cosmetics in the form of W / O emulsion were prepared using the composite particles prepared in Examples 1 to 6 and Comparative Example 1, respectively The basic composition is shown in Table 1 below.

Furtherance Content (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Alkyl benzoate 42.0 42.0 42.0 42.0 42.0 42.0 42.0 42.0 Silicone emulsifier (KF6027) 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Bentonite 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 ≪ RTI ID = 0.0 >
Polymer composite particle 12.0 12.0 12.0 12.0 12.0 12.0 - - The results obtained in the comparative example
Polymer composite particle - - - - - - 12.0 12.0 Distilled water 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0

The final products of Examples 1 to 6 were measured for particle size and shape using a particle size analyzer and a scanning electron microscope, and the W / O emulsions prepared in Formulation Examples 1 to 6 were dispersed in SPF 290 (Sun Protection Factor analyzer. The results are shown in Table 2 below.

As a result of measurement, spherical polymer particles having an average particle diameter of 4 to 5 mu m were observed in the comparative example, and in Examples 1 to 6 according to the present invention, the average particle diameter was 150 to 400 nm.

Further, 12% by weight of the powders of Examples 1 to 6 were added to prepare a W / O type cream, and ultraviolet shielding ability was measured. As a result, a very high PF (protection factor) value and an SPF (Sun Protection Factor) .

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Weight ratio (%) of polymer composite particles containing ultraviolet screening agent 12 12 12 12 12 12 12 12 Average particle diameter 286 nm 354 nm 206 nm 229 nm 262 nm 186 nm 4.3 μM 5.1 μM SPF 6.3 4.6 7.1 13.4 11.6 14.6 4.1 8.2 UVA PF 5.8 4.9 6.6 4.9 3.8 5.6 3.0 2.3

[Test Example 2] Skin irritation test

Twenty test subjects were skin patch tested using the UV-blocking cosmetics of Formulation Example 1 and Comparative Example 1 to test skin irritation. The results are shown in Table 3.

The product of Comparative Example 1 Products of Formulation Example 1 +++ 0 0 ++ 0 0 + 2 One ± 15 11 - 3 8 Total number of people 20 20 ※ Criteria
+++: Strong trouble, ++: Weak trouble,
+: Minor trouble, ±: Normal
- : voice

As can be seen from Table 3, it was confirmed that Formulation Example 1 was significantly superior to Comparative Example 1 in feeling.

Formulation Example 7

UV-blocking cosmetics in the form of a W / O emulsion were prepared using the polymer composite particles prepared in Example 1, and the basic compositions are shown in Table 8 below.

Furtherance Content (parts by weight) Formulation Example 7 W / O Micro Crystal Line Wax 3.0 Liquid paraffin 7.0 Silicone oil 6.0 Cyclopenta silicon 6.0 Paraben 0.1 Cetyl dimethicone copolyol 2.0 The results obtained in Example 1
Polymer nanocomposite particles 8.33 Butyl methoxydibenzoylmethane - Octylmethoxycinnamate - Ethylhexylmethoxyninite 7.0 Butyllene glycol 5.0 water 61.4

Formulation Example 8

UV-blocking cosmetics in the form of a W / O emulsion were prepared using the polymer composite particles prepared in Example 1, and basic compositions are shown in Table 5 below.

Furtherance Content (parts by weight) Formulation Example 8 W / O Beads wax 2.0 Stearyl alcohol 1.5 Stearic acid 0.5 Squalane 10.0 Polyoxyethylene ethyl ether 1.0 Propylene glycol monostearate 3.0 Ethyl hexylmethoxycinnamate 7.0 Paraben 0.1 The results obtained in Example 1
Polymer nanocomposite particles 8.33 Butyl methoxydibenzoylmethane - Octylmethoxycinnamate - Propylene glycol 8.0 glycerin 4.0 Preethylamine 1.0 water 59.4

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

a) dissolving and dispersing a chemical sunscreen agent in a radical polymerizable monomer and a polyfunctional crosslinking monomer, and adding an initiator to prepare a dispersion;
b) emulsifying the dispersion containing the chemical sunscreen agent in a solvent in the presence of a dispersion stabilizer to form droplets;
c) homogenizing the droplets using a high pressure homogenizer;
d) polymerizing the homogenized droplets to prepare polymer nanocomposite particles; And
e) washing and drying the polymer composite particles prepared above
Wherein the polymer nanocomposite particles have an average particle diameter of not more than 100 nm. The method according to claim 1,
Wherein the pressure of the high-pressure homogenizer of c) is 500 to 2000 bar. The method according to claim 1,
Wherein the pressure of the high-pressure homogenizer of the step c) is in the range of 0.1 to 10 μm. The method according to claim 1,
Wherein the a) chemical ultraviolet screening agent is 0.1 to 200 parts by weight based on 100 parts by weight of the radical polymerizable monomer and the polyfunctional crosslinking monomer. A polymer nanocomposite particle produced by the method according to claim 1. 6. The method of claim 5,
The polymer nanocomposite particles
a) a polymer particle having a particle size of 10 to 800 nm in which a radically polymerizable monomer and a multi-functional crosslinking monomer are polymerized; And
b) a polymeric nanocomposite particle wherein a chemical ultraviolet screening agent is bound to the inner surface of the polymer particle. A cosmetic composition for protecting ultraviolet rays, which comprises the polymer nanocomposite particle of claim 5 as an active ingredient. 8. The method of claim 7,
Wherein the cosmetic composition contains 0.01 to 30% by weight of polymer nanocomposite particles containing an ultraviolet screening agent based on the total weight of the composition.