WO2018062742A1

WO2018062742A1 - Polymer beads, preparation method therefor, and cosmetic product using same

Info

Publication number: WO2018062742A1
Application number: PCT/KR2017/010200
Authority: WO
Inventors: 김영신; 유설아
Original assignee: 코오롱인더스트리 주식회사
Priority date: 2016-09-30
Filing date: 2017-09-18
Publication date: 2018-04-05
Also published as: KR20180036383A; KR102381991B1; WO2018062742A8; KR102381991B9

Abstract

The present invention relates to: polymer beads having uniform particle shape and size, having miscibility of inner components and low dissolution characteristics, and having optical characteristics of selectively absorbing near infrared light; a polymer bead composite having optical characteristics of selectively absorbing near infrared light and ultraviolet light at the same time; an optical particle composition using the same; and a cosmetic product.

Description

[Explanation of invention]

[Name of invention]

Polymer beads, tooth manufacturing methods and cosmetics using the same

Technical Field

The present invention relates to a polymer bead, a manufacturing method thereof and a cosmetic using the same. More specifically, the polymer bead having a uniform shape and size of particles, having a high degree of miscibility and low elution characteristics of the internal components, and an optical characteristic of selectively absorbing light in the ultraviolet region, a method for preparing the same, and a method of using the same It's about supplies.

[Technique to become background of invention]

UV protection used in cosmetics consists of two types: physical blocking by inorganic substances and chemical blocking by organic substances, and based on the above concept, the sunscreen is based on the above concept. Divided into

In short, a physical sunscreen refers to a product consisting of t itanium dioxide or zinc dioxide, which blocks both UVA and UVB by reflecting the transmitted ultraviolet rays and blocks the pores, so it is often applied over time. It is not recommended, and the US FDA recommends that it is safe for the skin and can be applied to babies. However, there is a disadvantage that the skin spreadability is poor compared to the light male male organic material, and there is a clouding phenomenon.

Next, the organic sunscreen refers to all components except the above physical sunscreen, and the organic compound absorbs ultraviolet rays and converts them into thermal energy so that the ultraviolet rays do not reach the skin. In addition, organic sunscreens have the advantages of no whitening and good applicability and absorption. However, since the organic compound is directly in contact with the skin, it may cause skin trouble in sensitive skin, and the organic sunscreen ingredients are frequently oxidized, so they need to be frequently applied. As such, conventional sunscreens are not harmful to the skin, but are limited to inorganic sunscreens due to their application properties and cloudiness. However, because it uses organic sunscreen, which is limited in use due to the harmfulness of the skin, there is a need for an alternative to solve the problem.

[Content of invention]

Problem to be solved

The present invention is to provide a polymer bead having a uniform shape and size of particles, having a high degree of compatibility and low dissolution properties of the internal components, and having an optical property to selectively absorb light in the ultraviolet region.

In addition, the present invention is to provide a method for producing the polymer beads.

In addition, the present invention is to provide a cosmetic using the polymer beads.

[Solution of problem]

In the present specification, a polymer resin including a vinyl repeating unit derived from a vinyl monomer; And a photo-reflective organic material bonded to the polymer resin and having a maximum light absorption wavelength at a wavelength of 280 nm to 400 nm, wherein a polymer bead having a content of vinyl monomer remaining in the high molecular resin is 100 ppm or less is provided.

The present invention also provides a method for preparing a suspension comprising: stirring a semi-aqueous solution containing a vinyl monomer, a photo-reflective organic material having an maximum light absorption wavelength at a wavelength of 280 nm to 400 nm, and an initiator; And polymerizing the suspension, wherein the polymerizing of the suspension comprises: subjecting the suspension to 4 (the first polymerization step performed for 5 to 7 hours at a temperature of rc to 60 ^° C.); Provided is a method for producing polymer beads, comprising a second polymerization step wherein the result of the first polymerization step is carried out for 3 to 5 hours at a temperature of 80 ^° C to 100 ^° C.

In the present specification, a cosmetic including the polymer beads is provided.

Hereinafter, a polymer bead according to a specific embodiment of the present invention, a manufacturing method thereof, and a cosmetic using the same will be described in detail. In the present specification, (meth) acrylic acid is meant to include both acrylic acid and methacrylic acid.

In the present specification, (meth) acrylate is also meant to include both acrylates and methacrylates. According to one embodiment of the invention, a polymer resin including a vinyl repeating unit derived from a vinyl monomer; And a photoreactive organic material bonded to the polymer resin, the photoreactive organic material having a maximum light absorption wavelength at a wavelength of 280 nm to 400 ran, wherein the content of the vinyl monomer remaining in the polymer resin is 100 ppm or less. have.

By using the polymer beads described above, the present inventors include an optical semi-aung organic material that absorbs light in the ultraviolet region and converts it into a form of thermal energy inside a spherical particle of uniform size, so that the optical properties of the The same was realized in the polymer beads, and the experiments confirmed that the photoreactive organic material may have excellent miscibility and durability in the beads and completed the invention.

In particular, the polymer bead can be tightly bonded to the polymer resin on the bead of the photo semi-finished organic material contained therein is highly soluble to the vinyl monomer, and the excellent performance by preventing the transition of the photo semi-finished organic material Weather resistance and durability can be secured. Accordingly, since the photo-banung organic material is stably bound in the polymer bead, the photo-reflective organic material is exposed to the outside of the bead, thereby making it difficult to directly contact the skin, thereby preventing skin damage.

In addition, the polymer beads can be effectively dispersed in the binder resin or the solvent without any reaction, while maintaining the spherical particle shape of a uniform size, ensuring stable performance in various technical applications I can send it.

The polymer beads may have a maximum light absorption wavelength at a wavelength of 280 nm to 400 ran. The maximum light absorption wavelength means a wavelength value showing the highest light absorption as a result of measuring light absorption according to the wavelength. Light absorption Means the ratio of the actual measured absorbance to the maximum measurable absorbance, and as shown in Table 2 below, the maximum measurable absorbance is 2.0.

The polymer beads may have a maximum value of light absorption at a wavelength of 280 nm to 400 nm. For this reason, the polymer beads may have a selective absorbing ability for light in a specific ultraviolet region.

In addition, the polymer beads may have a light absorption of 0.05% or less, or 0.001% to 0.05% at an ultraviolet wavelength of 200 nm or less, 450 nm or more. As described above, the light absorbance means the ratio of the actual measured absorbance to the maximum measurable absorbance, and as shown in Table 2 below, the maximum measurable absorbance is 2.0.

The polymer beads exhibit very low values of absorbances of less than 0.05 and almost zero at ultraviolet wavelengths of 200 nm or less and 450 nm or more, from which the polymer beads hardly absorb light in other ultraviolet regions. Can be.

The polymer beads may comprise a photoreactive organic material. The light semi-aung organic material may be a material that absorbs light and converts it into thermal energy.

Specifically, the photoreactive organic material may include at least one selected from the group consisting of a triazine compound and a benzoyl compound.

The triazine-based compound includes a triazine or a derivative of triazine, and the derivative refers to a similar compound obtained by chemically changing a part of a compound, and usually a hydrogen atom or a specific atom group in a compound is attached to another atom or group of atoms. It refers to the compound substituted by.

Specifically, the triazine-based compound may include a triazine and an alkoxy substituted aryl group bonded to the triazine. In the alkoxy-substituted aryl group bonded to the triazine, the aryl group may include a phenyl group or a hydroxyphenyl group, and the alkoxy group substituted with the aryl group may be a linear or branched alkyl group having 1 to 20 carbon atoms and an oxygen atom bonded thereto. As the functional group in the form, for example, methoxy, ethoxy, propoxy, appendix, pentoxy, nucleosiloxy, heptyloxy, octyloxy, Ethyl nucleosil, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy tetradecyloxy, pentadecyloxy, nuxadecyloxy, heptadecyloxy, octadecyloxy nonadecyl C, eicosanyloxy, or all possible isomers thereof, but may not be limited thereto.

More specifically, the alkoxy substituted aryl group may be bonded to a carbon atom included in the triazine, and one or more alkoxy substituted aryl groups may be independently bonded to a carbon atom included in the triazine.

More preferably, the triazine-based compound may include a triazine and one hydroxy substituted phenyl group and two ethylnuxyloxy substituted hydroxyphenyl groups bonded to the triazine. More specific examples of the triazine-based compound include Ti nosorb S (b i s-e t hy 1 hexy 1 oxypheno 1 methoxyphenyl t r i az ine).

The benzoyl compound refers to a compound including a benzoyl functional group in a molecular structure, and specifically, the benzoyl compound may be a dibenzoyl compound containing two benzoyl functional groups.

Specifically, the dibenzoyl compound may include dibenzoyl alkanes in which two benzoyl functional groups are bonded to an alkane compound having 1 to 10 carbon atoms. The dibenzoyl alkanes include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, and 6 to 6 carbon atoms. Selected from the group consisting of 12 arylalkyl groups, halogen atoms, cyano groups, amino groups, amidino groups, nitro groups, amide groups, carbonyl groups, hydroxyl groups, sulfonyl groups, carbamate groups, and alkoxy groups having 1 to 10 carbon atoms It may be substituted by one or more functional groups.

The term "substituted" means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent may be substituted, and when two or more are substituted, 2 The above substituents may be the same or different from each other.

More specifically, the dibenzoyl alkane may be substituted by an alkoxy group having 1 to 5 carbon atoms and a branched alkyl group having 4 to 10 carbon atoms. Preferably one small each of the two benzene rings contained in the dibenzoyl alkanes. The vessel may be replaced. For example, one of two benzene rings included in the dibenzoyl alkanes may be substituted with an alkoxy group having 1 to 5 carbon atoms, and another branched alkyl group having 4 to 10 carbon atoms may be substituted with the other one.

Examples of positions at which the alkoxy group having 1 to 5 carbon atoms and the branched alkyl group having 4 to 10 carbon atoms are substituted are not particularly limited, and for example, ortho, meta of benzoyl functional groups contained in the dibenzoyl alkanes, for example. Or may be substituted at the para position, and preferably substituted at the para position. Examples of the alkoxy group having 1 to 5 carbon atoms include meso groups, examples of branched alkyl groups having 4 to 10 carbon atoms include t-butyl group, and more specific examples of the benzoyl compound include Parsol 1789 (t -Butyl). Methoxy di benzoyl me thane).

In addition, the photo-reflective organic material may include materials commonly used in the cosmetics market. Examples of the photo-banung organic substance include P-aminobenzoic acid, Padimate 0, Phenylbenzimidazole sul fonic acid, Sinoxate and Dioxy benzone. (Dioxybenzone), Oxybenzone, Homosalate, Methyl anthrani late, Octocrylene, Octyl methoxyinnamate, Octyl salicylate (Octyl sal icylate), Sul i sobenzone, Trol amine sal i cylate, Abobenzone, Ecamsule, 4-Methylbenzyl idene camphor , Tinosorb M, Mesoryl XL, Benzophenone-9, Uvinul T150, Parsol SLX, Uvinul A Plus Plus), Uvasorb HEB, isopentyl-4-methoxycinnamate (Isopentenyl-4 -me t hoxyc i nnama t e).

The photo semi-finished organic material may have a solubility in vinyl monomers of 30% to 100%, or 50% to 100%, or 60% to 100%. As such, since the photo-reflective organic material may have high solubility with respect to the vinyl monomer, it may be dissolved in the vinyl monomer to implement excellent optical properties and durability. When the solubility of the light semi-animal organic material in the vinyl monomer is less than 30%, the light semi-animal organic material may not be dispersed stably and uniformly, and a phenomenon may occur in the final bead surface.

The content of the photoreactive organic substance with respect to the polymer beads may be 5% by weight to 90% by weight, or 30% by weight to 50% by weight. When the content of the photo-reflective organic material to the polymer beads is excessively increased, the solubility of the photo-reflective organic material may be reduced to cause aggregation during polymer bead polymerization, and when the content of the photo-reflective organic material is excessively reduced, desired UV blocking ability Can not get the effect.

The photo-reflective organic material may exhibit excellent UV blocking ability as described above when formulated into a cosmetic formulation. In addition, even after being supported in the fiber bead, it may exhibit the same light absorption wavelength peak as the light absorption wavelength peak which is inherently characteristic of the light reflective organic material.

Specifically, the light semi-reflective organic material may have a maximum light absorption wavelength at a wavelength of 280 ran to 400 ran. In addition, the photoreactive organic material may have a light absorption of 0.05% or less at an ultraviolet wavelength of 200 nm or less and 450 nm or more.

In addition, the polymer beads may include a polymer resin including a vinyl-based repeating unit derived from a vinyl monomer. The vinyl repeating unit means a repeating unit included in a homopolymer of a vinyl monomer, which is a compound containing a carbon-carbon double bond in a molecule, that is, a repeating unit derived from a vinyl monomer. Examples of the vinyl monomers are not particularly limited, for example, an aromatic vinyl compound, a (meth) acrylic acid alkyl ester compound having 1 to 20 carbon atoms, a (meth) acrylic acid fluoroalkyl ester compound having 1 to 20 carbon atoms, or these It may include two or more combinations of. Moreover, the polyfunctional (meth) acrylate type compound mentioned later may further be included.

Examples of the aromatic vinyl compound are not particularly limited, but for example, styrene or divinyl benzene may be used.

Examples of the (meth) acrylic acid ester compound having 1 to 20 carbon atoms are also not particularly limited. For example, methyl (meth) acrylate, ethyl (meth Ta) acrylate, butyl (meth) acrylate, trimethylolmethane tetraacrylate, trimethylmethane triacrylate, trimethylolbutane triacrylate, ethylene glycol dimethacrylate or two or more kinds thereof Can be used.

Examples of the C1-20 acrylic acid or methacrylic acid fluoroalkyl ester compound include fluoromethyl (meth) acrylate, fluoroethyl (meth) acrylate, and fluorobutyl (meth) acrylate. Or two or more kinds thereof.

Meanwhile, the polymer resin may further include a repeating unit derived from a polyfunctional (meth) acrylate-based compound. The repeating unit derived from the polyfunctional (meth) acrylate-based compound means a repeating unit included in the homopolymer of the polyfunctional (meth) acrylate-based compound, and examples of the polyfunctional (meth) acrylate-based compound are largely limited. For example, 1, 2-ethanediol diacrylate, 1, 3-propanediol diacrylate, 1, 3-butanediol diacrylate, 1, 4-butanediol diacrylate, 1,5- Pentanediol diacrylate, 1, 6-nucleic acid diol diacrylate divinylbenzene, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate ， Polypropylene glycol diacrylate ， Polybutylene glycide diacrylate ， Allyl acrylate ， 1,2-ethanediol dimethacrylate 1,3-propanedioldimethacrylate, 1,3-butanedidimethacrylate, 1,4-butanedidimethacrylate, 1,5-pentanedioldimethacrylate, 1, 6-hexanediol Dimethacrylate, Ethylene Glycol Dimethacrylate, Propylene Glycol Dimethacrylate, Butylene Glycol Dimethacrylate, Triethylene Glycol Dimethacrylate, Polyethylene Glycol Dimethacrylate, Polypropylene Glycol Dimethacrylate Elate, polybutylene glycol dimethacrylate, allyl methacrylate, diallyl maleate or a combination of two or more thereof can be used.

The content of the repeating unit derived from the multifunctional (meth) acrylate-based compound may be 10 to 95 parts by weight based on the total polymer beads.

Meanwhile, the content of the vinyl monomer remaining in the polymer resin may be 100 ppm or less, or 10 ppm to 50 ppm, or 13 ppm to 43 ppm. The polymer resin may further include a vinyl monomer which does not form some polymerization together with the vinyl repeating unit obtained through homopolymerization of the vinyl monomer, and thus the content of the vinyl monomer remaining without forming the polymerization may be Can be measured in very small quantities. As such, since a small amount of non-banung monomer is detected in the final polymer beads, it may be advantageous for use as a cosmetic bead because there is less skin hazard. Examples of the vinyl monomer remaining in the polymer resin include the above-mentioned aromatic vinyl compound, a (meth) acrylic acid alkyl ester compound having 1 to 20 carbon atoms, a (meth) acrylic acid fluoroalkyl ester compound having 1 to 20 carbon atoms, and a polyfunctional compound. It may contain a (meth) acrylate type compound or two or more kinds thereof.

The shape of the polymer beads is not particularly limited, and examples thereof include spherical shape, non-spherical shape, monocyte shape, millet shape, and the like. In addition, the average particle diameter of the polymer beads may be 1 / ΛΠ to 500 mi, or may be from 2 IM to 60.

The polymer beads may have a variation coefficient of 10% to 40¾> obtained by Equation 1 below. Accordingly, the polymer beads can maintain spherical and non-spherical shapes in a uniform size.

[Equation 1]

Coefficient of variation (%) = (standard deviation of particle size / average particle diameter of beads) X 100

On the other hand, if the coefficient of variation of the polymer bead is excessively increased to more than 40%, coarse particles are generated due to coagulation, which may result in poor elution and compatibility when applied to cosmetics.

In addition, the polymer bead may be widely used as a sunscreen for cosmetics as well as construction and plastic additives that require UV protection. On the other hand, according to another embodiment of the present invention, a suspension is prepared by stirring a semi-aqueous solution containing a vinyl monomer, a photobanung organic material having an maximum light absorption wavelength and an initiator _at a wavelength of 280nm to 400nm; And polymerizing the suspension, and polymerizing the suspension comprises: The suspension is run for 5 to 7 hours at a temperature of 40 ^° C to 60 ^° C.

1 polymerization step; And the resultant of the first polymerization step at 8 (rc to ioo ^° c)

There can be provided a method for producing polymer beads, including a system dipolymerization step that proceeds for 3 to 5 hours.

The reaction solution may include a vinyl-based monomer, an optical reaction organic material having an maximum light absorption wavelength at a wavelength of 280 nm to 400 nm, and an initiator. The content of the vinyl-based monomer and the photo-reflective organic material includes the content described above in the embodiment.

10 parts by weight to 80 parts by weight of the light semi-cyclic organic material may be added based on 100 parts by weight of the vinyl monomer. When the content of the photo-reflective organic material to the vinyl monomer is excessively increased, the solubility of the photo-reflective organic material may be reduced, thereby causing aggregation during polymer bead polymerization, and when the content of the photoreactive organic material is excessively reduced, desired UV blocking ability Can not get the effect. The initiator is a compound capable of initiating polymerization by pyrolysis on a semi-aqueous solution, for example, 2, 2-azobisisobutyronitrile, 4, 4-azobis (4) -cyanopentanoic acid, 2, 2 Azo initiators such as -azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide Peroxide-based compounds such as octanoyl peroxide and di cumyl peroxide. The reaction solution may further include a polyfunctional (meth) acrylate compound, a suspension stabilizer, an aqueous solvent, or a mixture of two or more thereof.

Examples of the polyfunctional (meth) acrylate-based compound are not particularly limited, for example, 1,2-ethanedididiacrylate, 1,3-propanediol diacrylate, 1,3-butanedioldi Acrylate 1, 4- butanediol diacrylate, 1, 5- pentanediol diacrylate, 1, 6- di nucleic acid diacrylate, divinylbenzene, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol Diacrylate, Triethylene glycol diacrylate, Polyethylene glycol diacrylate, Polypropylene glycol diacrylate, Polybutylene glycol diacrylate, Allyl acrylate, 1, 2-ethanediol dimethacrylate, 1 , 3-propanediol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-nucleic acid dimethacrylate, ethyleneglycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol dimethacryl Elate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, allyl methacrylate, diallyl maleate or a combination of two or more thereof may be used.

The weight ratio of the vinyl monomer and the polyfunctional (meth) acrylate compound may be 2: 1 to 10: 1, or 5: 1 to 8: 1.

Examples of the suspension stabilizer are not particularly limited, but for example, polyvinyl pyridone, polyvinyl methyl ether, polyethyleneimine, polymethyl methacrylate acrylic acid copolymer, polyvinyl alcohol, vinyl acetate copolymer, ethyl Salose, hydroxypropylsalose or a combination of two or more thereof can be used.

The aqueous solvent may include water or a hydrophilic solvent, and preferably ion exchanged water may be used. The ion-exchanged water mainly means water purified by ion-exchange method, and preferably has a small amount of positive ions, and may use ultrapure water having a resistance of 5 MΩ or more under a nitrogen stream generated through an ion exchanger.

The polymer bead production method may include the step of suspension polymerization of the reaction solution. Examples of the suspension polymerization step are not particularly limited, for example, preparing a suspension by stirring the reaction solution; And polymerizing the suspension solution. The suspension means a liquid in which solid fine particles are dispersed.

Specifically, the stirring step of the stirring solution is a first stirring step of stirring for 20 to 60 minutes at a speed of 500rpm to l, 000rpm; And a stirring step of stirring for 1 minute to 20 minutes at a speed of 5,000 rpm to 15,000 rpm.

In the first stirring step of stirring the reaction liquid at a speed of 500 rpm to l, 000 rpm, or 800 rpm to 10 rpm, for 10 minutes to 60 minutes, or 20 minutes to 40 minutes, if the stirring speed is not high enough, Fusion can make it difficult to form stable particles. Although the example of the specific stirring method of performing the first stirring step is not particularly limited, for example, the method may be used by adding the semi-agitator to the reaction vessel and using a mechanical stirrer.

After the first stirring step, 5,000 rpm to 15,000 rpm, or lO. The second stirring step of stirring at 1 to 20 minutes, or 5 to 15 minutes at a speed of OOOrpm to 14,000rpm can be performed.

Without the second stirring step, if polymerized immediately after the first stirring step, not only coagulation occurs but also polymer beads having a very large particle distribution can be prepared.

Although the example of the specific stirring method for proceeding the second stirring step is not limited to a large amount, for example, a method of discharging the semi-agitated solution, which has undergone the first stirring step, from the reaction vessel and stirring it through a homomixer (Homomixer) may be used. Can be.

The step of polymerizing the suspension may include: subjecting the suspension to 40 ^° C. to 6 ^° C. (first polymerization step being performed for 5 to 7 hours at a temperature of C; and 80 ^° C to 100 ^° C. of the resultant polymerization process). The polymerization may be performed for 3 to 5 hours at a temperature of C. The polymerization rate should be maintained at an appropriate level so that the polymer beads generated during the polymerization reaction do not settle down. The stirring speed may be performed at 100 to 300 rpm.

Without the crab dipolymerization step, when only the crab 1 polymerization step is carried out, unreacted monomers are not removed and a large amount of residual monomers are generated in the final polymer beads.

In addition, after the step of polymerizing the suspension, filtration, washing and drying may further include a step. The filtration, washing and drying methods can be used without limitation various methods commonly used.

However, in order to remove the unbanung monomer in the washing to the maximum, and to minimize the generation of residual monomer in the final polymer beads, specifically, for example, the first washing step with a strong base compound, the second washing step with an aqueous alcohol solution , And the third washing step with distilled water can be performed sequentially.

Examples of the strong base compound include potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium hydroxide and the like, and the aqueous alcohol solution contains 1 carbon atoms. G5 monohydric alcohols such as ethanol and water combinations may be used. Examples of the cleaning time are not particularly limited, but, for example, the first washing step and the second washing step may be performed for 3 to 5 hours, respectively.

In addition, after the drying step, a grinding step may be further included as necessary. Examples of the grinding method may include a grinder such as a jet mill, a ball mill atomizer or a hammer mill. On the other hand, according to another embodiment of the invention, there may be provided a cosmetic comprising the polymer bead of the embodiment. The cosmetics can realize the optical properties of the polymer beads of the embodiment, for example, UV protection properties as it is in the cosmetic product as well as low dissolution properties, excellent compatibility and high stability to the skin.

The content of the polymer beads may include the content described above with respect to the embodiment.

Examples of the content of the polymer beads included in the cosmetics are not limited to a large amount, for example, may be contained in 0.1 to ¾> to 10% by weight relative to the total cosmetic weight.

Examples of the form of the cosmetics are not particularly limited, for example, it may have a solid, liquid, wax, gel or cream.

In addition, the cosmetics are commonly used in the field of cosmetics, for example, water, preservatives, photo semi-finished organic substances, dyes with a coloring effect, thickeners, fragrances, alcohols, polyols, esters, electrolytes, gel formers, silicones It may further comprise a cosmetic adjuvant and a carrier such as an oil, a polymer, a copolymer, an emulsifier, a stabilizer and the like. In addition, the cosmetics may further include cosmetic activators such as, for example, organic and inorganic sunburn agents, moisturizers, enzymes and other vegetable active agents.

【Effects of the Invention】

According to the present invention, a polymer bead having a uniform shape and size of particles, an internal component having a low dissolution property and an optical property of selectively absorbing light in the ultraviolet region, a manufacturing method thereof, and a cosmetic using the same Can be provided.

[Brief Description of Drawings]

Figure 1 shows the surface FE-SEM image of the polymer beads obtained in Example 1.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the present invention, the content of the present invention is not limited by the following examples. Examples 1 to 3: Preparation of Polymer Beads

Reality U

369.6 g of methyl methacrylate (MMA), 50.4 g of ethylene glycol dimethacrylate (EGDMA) as a crosslinking agent, TinosorbS (bi s- et hy 1 hexy 1 oxypheno 1 methoxyphenyl tr iazine) (BasF) G) 184.8g (50% by weight of monomer), and 2g of azobisisobutyronitrile (AIBN) was added thereto as an initiator and mixed. Then, add 937.66 g of ion-exchanged water as a dispersion medium and dissolve 10 g of polyvinyl alcohol (Mw = 10, 000) in a reaction vessel, inject the mixture into the solution and use a mechanical stirrer at 900 rpm. Stirred for 30 minutes to prepare a premixing solution. After discharging the premixing solution, a homogenization process was performed to homogenize and emulsify at 12000 rpm for 10 minutes using a homomixer to prepare an emulsion.

Thereafter, the emulsion was added to a 2L reactor and the first suspension polymerization reaction was carried out at 50 ^° C. for 6 hours while stirring at a speed of 200 rpm under a nitrogen atmosphere, and the temperature was raised to 90 ^° C. for 2 hours, followed by a crab suspension suspension reaction for 4 hours. It was.

After filtering the polymer synthesized by the reaction using 200 mesh,

After adding K0H to 1% of the total polymerization solution, the mixture was stirred at 400 rpm for 4 hours to carry out a first wash. After the first washing, dehydration was performed, and the dehydrated cake was dispersed in a solution in which ethane and water were mixed one-to-one, and then mixed at 400 rpm for 4 hours or more to carry out a second washing. After completion of the second wash, filter, wash twice with DIW and filter the filtrate in a vacuum oven to dry for one day. Was prepared. Example 2

Polymer beads were prepared in the same manner as in Example 1, except that styrene monomer was used instead of methyl methacrylate. Implementation ^] 3

Polymer beads were prepared in the same manner as in Example 1, except that 110.88 g (30% by weight of monomer) of TinosorbS (bis-ethyl hexy 1 oxypheno 1 methoxyphenyl triazine) was used as a photobanung organic material. .

Comparative Examples 1 to 2: Preparation of Polymer Beads

Comparative Example 1

Polymer beads were prepared in the same manner as in Example 1, except that TinosorbS (bis-ethylhexyloxyphenol methoxyphenyl triazine) was not used as a photobanung organic material. Comparative Example 2

Polymer beads were prepared in the same manner as in Example 1, except that only one suspension polymerization reaction was performed for 6 hours at 50 ^° C. during the polymerization of the emulsion.

Experimental Example: Measurement of physical properties of polymer beads obtained in Examples and Comparative Examples The physical properties of the polymer beads obtained in Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 to 3, respectively. Experimental Example 1 Average particle size and coefficient of variation (CV) The average particle diameter and the variation of the polymer beads obtained in the above Examples and Comparative Examples using a particle size distribution measuring device (Colter Electronics, Multisizer4) Coefficients were measured and the results are shown in Table 1 below. The variation coefficient CV was obtained by the following equation.

[Equation 1] _

Coefficient of variation (¾) = (standard deviation of particle size / average particle diameter of beads) X 100. Experimental Example 2: Measurement of surface properties

For the polymer beads obtained in the above Examples and Comparative Examples, surface SEM images were taken using a Hitachi S-4300 apparatus, the surface properties were determined under the following criteria, and the results are shown in Table 1 below.

"Good": Bead formation is visually confirmed by SEM image

"Poor": Bead formation was not visually confirmed through the SEM image Experimental Example 3: Product yield measurement

For the polymer beads obtained in the above examples and comparative examples, after hot air drying at a temperature of 75 ^° C. for 24 hours, the yield was measured, and the results are shown in Table 1 below. Experimental Example 4: Residual Monomer Analysis

For the polymer beads obtained in the above Examples and Comparative Examples, the content of unbanung monomer was analyzed through GC analysis, and the results are shown in Table 1 below. Sample preparation and experimental conditions for the GC analysis are as follows.

-Sample preparation: A supernatant obtained by mixing the polymer bead sample with ethanol at a concentration of 20 > to detect the residual methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) content was 0.45.飄 It injected through the PTFE Syringe Filter. Standards of methyl methacrylate (MMA) and ethylene glycol di methacrylate (EGDMA) were analyzed by dilution in Ethan.

Experimental conditions

Instalment: Agilent GC-FID 6480A

Stationary Phase: DB-5MS (30m x 0.25 醒 x 0.25 醒)

. Mobi le Phase: He, 1 ml / min Temp. Program: From 40 ° C, 3 min to 280 ° C (@ 20 ° C / min)

Injection: 250 ° C, 0.4ul

Detector: FID, 280 ° C

Time: 20 min

Table 1

Results of Experimental Examples 1 to 4

As shown in Table 1, as the beads having a polymer specific average particle size of about 4 prepared in Examples 1 to 3, it was confirmed that the coefficient of variation (CV) has a particle size distribution of 25% to 29% and product yield Was found to be good as 90% or more. In addition, it was confirmed that the residual monomers were analyzed to 50 ppm or less, which is the allowable value in the cosmetic composition.

On the other hand, in the polymer beads of Example 2, it was confirmed that the particle size, the yield, and the like did not change even when different types of monomers (styrene) were added.

On the other hand, if the second suspension polymerization proceeds up to 90 ° C as in Comparative Example 2, the non-banung monomers are not removed, a large amount of the non-banung monomer is detected in the final polymer beads as cosmetic beads The use of was found to be inappropriate. Experimental Example 5: Absorbance

The polymer beads obtained in the above examples and comparative examples were mixed with Ethan, followed by absorbance measurement instrument (UV-Vis Spectroscopy, Thermo Fisher Scientific) The absorbance was measured using EVOLUTION 600), and the results are shown in Table 2 below. At this time, the content of the polymer beads in the total mixture was 0.01%.

Table 2

Results of Experiment 5 [Measurable maximum absorbance is 2.0]

As shown in Table 2, in the case of the polymer beads of Examples 1 to 3 carrying the photo-reflective organic material, the maximum absorption wavelength and the maximum absorption were found to be between 280 nm and 400 nm, and the maximum absorbance was It was confirmed that it can be used as a sunscreen at 1.7 or higher. On the other hand, the polymer bead of Comparative Example 1 containing no photoreactive organic material was not measured for the maximum absorption wavelength.

Accordingly, in the case of the polymer beads containing the photo-reflective organic material, it was confirmed that the UV blocking ability is maintained even after the photo-reflective organic material is beaded. Experimental Example 6 UV Protection Properties

SPF-290S equipment (0) 1 after preparation with a polymer bead content of 2% in the sunscreen of the lotion formulation in order to confirm the UV-blocking effect of the polymer beads obtained in the above Examples and Comparative Examples; 01 ^ 1: 1 ^" ^: 3, Inc.) was used to measure through SPF (Sun Protect i on Factor) and PFA (Protect ion Factor of UVA) values, which are shown in Table 3 below.

The SPF index indicates the degree of blocking ultraviolet B (UVB) having a wavelength of 290 to 320ran, and the higher the SPF index, the higher the blocking effect. Specifically, the SPF index is the minimum amount of erythema of the skin with sunscreen (the minimum amount of ultraviolet light (MED) that causes reddish erythema (redder skin), MED) to the minimum amount of erythema of the skin without sunscreen. It means divided value. The PFA index indicates the degree of blocking ultraviolet rays A (UVA) having a wavelength of 320 to 400 nm, and the higher the PFA index value, the higher the blocking effect. Specifically, the PFA index means a value obtained by dividing the minimum sustained instantaneous amount of instantaneous sunburn (MPPD) value of the skin with sunscreen by the minimum sustained instantaneous amount of skin without sunscreen. do.

Table 31

Results of Experimental Example 6

Reference Example: BasF, a sunscreen used in the experiment, as shown in Table 3, targeting only TinosorbS (BasF) as a photo-reflective organic material

When the relative comparison with TinosorbS as a reference, Examples 1 to 3 were evaluated to have similar levels. However, Comparative Example 1 can confirm that the SPF and PA value is lower than the reference example. Experimental Example 7: Sunscreen Elution and Formulation Compatibility Test

Using the sunscreen formulation of Experimental Example 6 was carried out a sunscreen dissolution test and formulation compatibility test, the results are shown in Table 4 below. The test evaluated the change of the formulation after leaving the sunscreen formulation at room temperature, low temperature (0 ^° C), high temperature (90 ^° C) for 14 days under the following criteria.

-Dissolution test: According to the presence or absence of a grain to be touched when the formulation is touched by hand, it is divided into 0, X (0: the grain is touched, X: the grain is not touched)

Compatibility test: Visually check the formulation to see if the layers D 0, separated by X (0: no delamination; X: no delamination)

[Table 4]

Results of Experimental Example 7

Reference example: Only TinosorbS (BasF) as a photo-reflective organic substance

As shown in Table 4, when the relative comparison with BasF TinosorbS, a sunscreen used in the experiment as a reference example, it was confirmed that Examples 1 to 3 there is no dissolution phenomenon at 0 ^° C, room temperature, 90. However, dissolution phenomenon was observed in Reference Example and Comparative Example 3. This is a phenomenon in which the photoreactive organic material reacts with other additives in the formulation. Beads carrying the photoreactive organic material in the beads, as in Examples 1 to 3, can prevent this dissolution and thus skin stability. You can expect the effect of.

In addition, Examples 1 to 3 carrying the photo-reflective and organic materials were confirmed that the layers were not separated even after 14 days of preparation of the formulation. In the Reference Example and Comparative Example 2, the phenomenon of the layers were separated due to the optical semi-active organic material was observed. Due to the change in the formulation, it was confirmed that the reference example and Comparative Example 2 can not be used in the actual cosmetic formulation.

Claims

[Claim]

[Claim 1]

Polymer resins including vinyl repeating units derived from vinyl monomers; And a photo-reflective organic material bonded to the polymer resin and having a maximum light absorption wavelength at a wavelength of 280 nm to 400 nm.

Polymer beads having a content of vinyl monomer remaining in the polymer resin of 100 ppm or less.

[Claim 2]

The method of claim 1,

Polymer beads having a coefficient of variation of 10% to 40% obtained by Equation 1 below:

[Equation 1]

Coefficient of variation (%) = (standard deviation of polymer bead particle size / average particle diameter of polymer bead) X 100.

[Claim 3]

The method of claim 1,

Based on the weight of the polymer beads, the content of the photo semi-finished organic material is 5% to 90% by weight, polymer beads.

[Claim 4]

The method of claim 1,

Said polymer beads having a maximum light absorption wavelength at a wavelength of 280 ran to 400 nm.

[Claim 5]

The method of claim 1,

The polymer beads are less than 200 ran, or less than 0.05% light absorption at a wavelength of 450 nm or more, polymer beads.

[Claim 6]

According to claim 1,

The photo-banung organic material comprises at least one selected from the group consisting of a triazine compound and a benzoyl compound, polymer beads.

[Claim 7]

According to claim 16,

Wherein said triazine-based compound comprises a triazine and an alkoxy substituted aryl group bonded to said triazine.

[Claim 8]

The method of claim 7,

The aryl group comprises a phenyl group or a hydroxyphenyl group, polymer beads.

[Claim 9]

The method of claim 6,

The benzoyl-based compound is a polymer bead comprising a dibenzoyl alkane wherein two benzoyl functional groups are bonded to an alkane compound having 1 to 10 carbon atoms.

[Claim 10]

The method of claim 19,

The dibenzoyl alkanes are substituted with an alkoxy group having 1 to 5 carbon atoms and a branched alkyl group having 4 to 10 carbon atoms, polymer beads.

[Claim 11]

According to claim 1,

The photo semi-finished organic material has a solubility in the vinyl monomer of 30% to 100%, polymer beads.

[Claim 12]

The method of claim 1,

The vinyl monomer includes at least one selected from the group consisting of an aromatic vinyl compound, a (meth) acrylic acid alkyl ester compound having 1 to 20 carbon atoms, and a (meth) acrylic acid fluoroalkyl ester compound having 1 to 20 carbon atoms, Polymer beads containing a (meth) acrylate type repeating unit.

[Claim 13]

Preparing a suspension by stirring a semi-aqueous solution comprising a vinyl monomer, a photoreactive organic substance having a maximum light absorption wavelength and an initiator at a wavelength of 280 nm to 400 nm; And polymerizing the suspension,

The step of polymerizing the suspension may include: 1 polymerizing the suspension at a temperature of 40 to 60 ^° C. for 5 to 7 hours; And dipolymerizing the result of the first polymerization step at a temperature of 80 ^° C. to 100 ^° C. for 3 hours to 5 hours.

[Claim 14]

The method of claim 13,

10 parts by weight to 80 parts by weight of the light semi-cyclic organic material is added based on 100 parts by weight of the vinyl monomer.

[Claim 15]

The method of claim 13,

The semi-aqueous solution further comprises one or more selected from the group consisting of a polyfunctional (meth) acrylate-based compound, a suspension stabilizer and an aqueous solvent, a method for producing polymer beads.

[Claim 16]

The method of claim 13,

The stirring step of the reaction solution is 20 minutes to a speed of 500rpm to l, 000rpm Stirring for 60 minutes to stir; And a second stirring step of stirring for 1 minute to 20 minutes at a speed of 5,000 rpm to 15, 000 rpm.

[Claim 17]

The method of claim 13,

Further comprising a washing step after the suspension polymerization step, a method for producing a polymer bead.

[Claim 181

The method of claim 17,

The washing step includes a first washing step with a strong base compound, a second washing step with an aqueous solution of alcohol, and a third washing step with distilled water. [Claim 19]

Cosmetics comprising a polymer bead of bran U.