KR20170038508A - Polymeric beads, polymeric beads complex, optical particle composition and cosmetics using the same - Google Patents

Abstract

The present invention relates to a method for selectively absorbing light of a polymer bead, a near-infrared ray region, and an ultraviolet ray region having uniform particle shape and size, excellent mechanical properties and heat resistance, and having optical properties for selectively absorbing light in a near- Polymeric bead complexes having optical properties, optical particle compositions using the same, and cosmetics.

Description

TECHNICAL FIELD [0001] The present invention relates to polymer beads, polymer beads, polymer beads, polymer beads, polymer beads, polymer beads, polymer beads,

The present invention relates to polymer beads, polymer bead complexes, optical particle compositions using the same, and cosmetics. More specifically, the present invention relates to a method of selectively absorbing light of a polymer bead, a near-infrared ray region, and an ultraviolet ray region having uniform shapes and sizes of particles, excellent mechanical properties and heat resistance and having optical properties that selectively absorb light in the near- , Optical particle compositions using the same, and cosmetics.

Polymer beads are collectively referred to as spherical particles having a uniform particle diameter distribution prepared by emulsion polymerization or suspension polymerization. Polymer beads have a wide variety of uses, and they are widely used not only for a light diffusion film, a protective film and a construction for a liquid crystal monitor but also for a transparent film for a color ink.

Polymer beads used for this purpose are generally manufactured by methods such as suspension polymerization, dispersion polymerization and emulsion polymerization.

In conventional suspension polymerization, polymer beads are prepared by dispersing monomers present in the aqueous phase by mechanical force. The polymer beads prepared by this method have a bead size of at least 100 mu m and the bead distribution tends to be wide because the beads are dispersed by the mechanical force.

Since the polymer beads produced through the conventional polymerization process have different refractive indexes from those of conventional resins, the polymer beads can provide hiding power, and thus they are widely used in extruding and manufacturing a light diffuser or a lighting fixture. As the product is made by extrusion, it is required to have excellent thermal stability because the product is used by mixing at a high temperature.

However, when such a conventional polymer bead is stagnated at high temperature for 30 minutes or more, the weight loss reduction width is large, which may lead to physical and chemical changes to the environment in which the bead is used. That is, there may be a change in physical properties of the final product due to lowered compatibility, fume or byproducts, and there is a problem in that physical properties such as the shape of the bead are seriously deformed when read by an SEM photograph.

Therefore, when applying to various applications such as a light diffusion film, it is possible to manufacture a polymer bead with improved thermal stability at high temperature so that generation of fume is minimized and property change is not caused even when a high temperature heat treatment step is performed in a manufacturing process Research on composition and process development that can be done is needed.

At the same time, there is also a need for research into composition and process development that can produce polymer beads that can meet industry needs for materials that can only react sensitively to light of a particular wavelength.

An object of the present invention is to provide a polymer bead having uniform particle shape and size, excellent mechanical properties and heat resistance, and optical properties that selectively absorb light in the near infrared region.

The present invention also provides a polymer bead conjugate having optical properties that simultaneously absorb light in the near-infrared region and ultraviolet region, using the polymer bead.

The present invention also provides an optical particle composition and cosmetic using the polymer bead or polymer bead complex.

In the present specification, at least one polymer resin selected from the group consisting of a polyvinyl resin, a polysiloxane resin and a polyurethane resin; And a colorant bonded to the polymer resin, wherein the polymer bead has a maximum absorption wavelength at a wavelength of 700 nm or more.

In the present specification, the polymer beads; And a plurality of metallic nanoparticles bonded to the surface of the polymer beads.

The present invention also provides an optical particle composition comprising at least one selected from the group consisting of the polymer beads and the polymer bead complex.

Also provided herein is a cosmetic comprising the optical particle composition.

Hereinafter, polymer beads, polymer bead complexes, optical particle compositions using the same, and cosmetics according to specific embodiments of the present invention will be described in detail.

In the present specification, (meth) acrylic acid means both acrylic acid and methacrylic acid.

In the present specification, (meth) acrylate is also meant to include both acrylate and methacrylate.

According to a first aspect of the present invention, there is provided a resin composition comprising: at least one polymer resin selected from the group consisting of a polyvinyl resin, a polysiloxane resin and a polyurethane resin; And a colorant bonded to the polymer resin, wherein polymer beads having a maximum absorption wavelength at a wavelength of 700 nm or more can be provided.

The inventors of the present invention have found that the use of the polymer beads described above allows the spherical particles having a uniform size to contain a coloring agent that absorbs light in the near infrared region and converts it into heat energy so that the optical characteristics of the coloring agent are also realized in the polymer bead At the same time, it has been confirmed through experiments that the thermal stability can be improved and excellent heat resistance can be obtained, and the invention is completed.

Further, the polymer beads are bonded to the polymer resin with the colorant contained therein, so that migration of the colorant can be prevented, and excellent weather resistance and durability can be secured. Further, excellent heat resistance can be ensured to such a degree that changes in physical properties of the polymer resin or the colorant can be prevented in a kneading or extruding process at a high temperature or a high pressure.

In addition, the polymer beads can be effectively dispersed in the binder resin or the solvent while maintaining the shape of the spherical particles of uniform size, so that stable performance can be secured in application to various technical fields.

Specifically, the polymer bead may have a maximum light absorption wavelength at a wavelength of 700 nm, or 750 nm to 1000 nm. The maximum light absorption wavelength means a wavelength value showing the highest light absorption rate as a result of measuring light absorption according to the wavelength. The light absorption rate means a ratio of the actually measured absorbance to the maximum measurable absorbance, and the maximum measurable absorbance is 2.0 as shown in Table 2 below.

As shown in FIG. 1, the polymer bead may have a maximum value of the light absorptance at a wavelength of 700 nm, or 750 nm to 1000 nm. Thus, the polymer bead can have a selective absorption capacity for light in the near infrared region of 750 nm to 1000 nm wavelength.

The polymer bead selectively absorbs light in the near infrared region having a wavelength of 750 nm to 1000 nm and then converts the light into thermal energy. As a result, the polymer bead can shield the light in the near infrared region having a wavelength of 750 nm to 1000 nm. In particular, recently, it has been revealed that infrared rays are one of environmental factors promoting skin aging phenomenon such as wrinkles, freckles, pigmentation, elastic loss, skin cancer, etc. Therefore, Aging can be prevented.

The polymer bead may have a light absorptivity of 10% or less at a wavelength of 450 nm to 650 nm. As described above, the light absorptance means a ratio of the actually measured absorbance to the measurable maximum absorbance, and the maximum measurable absorbance is 2.0, as shown in Table 2 below.

As shown in FIG. 1, the polymer bead shows a low value of absorbance at a wavelength of 450 nm to 650 nm of 0.2 or less, confirming that the polymer bead hardly absorbs light in the visible light region . That is, the polymer bead may have a selective absorption capacity for light in the near infrared region of 750 nm to 1000 nm wavelength.

Examples of the shape of the polymer beads are not limited to a wide range. For example, the shape of the polymer beads may be spherical, spherical, or polyhedral, and the cross section of the polymer beads may be circular, elliptical, or polygonal of 3 to 50. The average particle size of the polymer beads may be from 1 탆 to 500 탆, or from 2 탆 to 400 탆, or from 3 탆 to 300 탆, or from 3 탆 to 50 탆, or from 3 탆 to 10 탆.

The polymer bead may have a coefficient of variation of 20% to 50%, or 30% to 50%, obtained by the following formula (1). Accordingly, the polymer beads can maintain a spherical shape with a uniform size.

[Equation 1]

(%) = (Standard deviation of polymer bead diameter / average particle diameter of polymer bead) X 100

In addition, the polymer beads may include a colorant. As the coloring agent, a dye (Dye) or a pigment may be used, and a dye may be preferably used.

The colorant may have a maximum light absorption wavelength at a wavelength of 750 nm to 1000 nm. The maximum optical absorption wavelength means a wavelength showing the maximum optical absorption value on the optical absorption spectrum. The optical properties of the colorant may be embodied in a polymer bead mixed with a polymer resin. That is, the polymer bead may include a colorant, and may have a selective absorption capacity for light in a near-infrared region of a wavelength of 750 nm to 1000 nm.

The colorant may include at least one selected from the group consisting of a phthalocyanin compound, a cyanine compound, an anthraquinone compound, a dithiol compound, and a diimmonium compound.

The phthalocyanine compound, the cyanine compound, the anthraquinone compound, the dithiol compound, and the diimmonium compound may be used as a phthalocyanine compound, a cyanine compound, an anthraquinone compound, a dithiol compound, Or a derivative thereof. The derivative may be a substitution product in which a hydrogen atom contained in a phthalocyanin compound, a cyanine compound, a diimmonium compound or the like is substituted with a specific functional group Compounds or ionic compounds having the form of salts. The examples of the functional groups are not limited to a wide variety, and various known functional groups or atomic groups can be used without limitation.

Specifically, the cyanine-based compound may include a cyanine compound represented by the general formula (11) or a derivative thereof. The derivative of the cyanine compound means a compound obtained by substituting a part of the structure of the cyanine compound with another atom or atomic group.

(11)

In the formula (11), a hetero compound including nitrogen may be bonded to a portion indicated by a dotted line. Examples of the nitrogen containing hetero compound include benzoxazole, indole, quinoline, benzothiazole ) And the like.

The phthalocyanine compound may include at least one selected from the group consisting of a phthalocyanine compound, a naphthalocyanine compound, a metal-phthalocyanine complex, a metal-naphthalocyanine complex, and derivatives thereof.

The derivative means a compound obtained by substituting a part of the structure of a phthalocyanine compound, a naphthalocyanine compound, a metal-phthalocyanine complex and a metal-naphthalocyanine complex by another atom or atomic group. Examples of the substituent 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, A halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amido group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group, an alkoxy group having 1 to 10 carbon atoms, An alkoxy group and the like.

The phthalocyanine is a compound represented by the following formula (12), which is a molecular formula C ₃₂ H ₁₆ N ₃ H ₂ , and shows a structure similar to porphyrin, and can form a metal-phthalocyanine complex in which two H in the center are substituted by other metal ions have.

[Chemical Formula 12]

The naphthalocyanine compound may be a compound represented by the following formula (13). Like the above-mentioned phthalocyanine, a metal-naphthalocyanine complex in which two H in the central part are substituted by other metal ions can be formed.

[Chemical Formula 13]

More specifically, examples of the metal in the metal-phthalocyanine composite and the metal-naphthalocyanine complex or derivatives thereof are not limited to a great extent, but transition metals of Groups 3 to 12 can be used, for example. More specific examples of the transition metal include copper (Cu) and vanadium (V). The metal may be present in the form of a metal oxide combined with oxygen if necessary.

Specific examples of the metal-phthalocyanine complex and derivatives thereof include vanadium phthalocyanine-based compounds. The vanadium phthalocyanine compound means a vanadium phthalocyanine compound or a derivative thereof. Specifically, the vanadium phthalocyanine compound may be a compound represented by the following formula (14).

[Chemical Formula 14]

In the formula (14), R ₁₁ to R ₂₆ are the same or different and each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, An aryl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an alkynyl group having 1 to 20 carbon atoms.

The alkyl group is a monovalent functional group derived from an alkane, for example, a straight chain, branched or cyclic group such as methyl, ethyl, propyl, isobutyl, sec-butyl, Hexyl, and the like. Examples of the substituent 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 10 carbon atoms, A halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amido group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group Group, an alkoxy group having 1 to 10 carbon atoms, and the like.

The heteroalkyl group may be an alkyl group containing O, N or S as a heteroatom, and at least one hydrogen atom contained in the heteroalkylene group may be substituted with the same substituent as the alkyl group.

The aryl group is a monovalent functional group derived from arene, for example, monocyclic or polycyclic. Specific examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, and the like. Examples of the polycyclic aryl group include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, klycenyl, At least one hydrogen atom in each of these aryl groups may be substituted with the same substituent as the alkyl group.

The heteroaryl group may be an aryl group containing O, N or S as a heteroatom, and at least one hydrogen atom contained in the heteroalkylene group may be substituted with the same substituent as the alkyl group.

The alkenyl group or alkynyl group means that at least one carbon-carbon double bond or triple bond is contained in the middle or end of the alkyl group as defined above, and examples thereof include ethylene, propylene, butylene, Hexylene, acetylene, and the like. At least one hydrogen atom of the alkenyl group or alkynyl group may be substituted with the same substituent as the alkyl group.

The halogen may be an element of F, Cl, Br, I.

More specifically, in the above formula (14), R ₁₂ , R _13, R _16, R _17, R _20, R ₂₁ R ₂₄ and R ₂₅ are each independently OR _a , SR _b or a halogen atom, of which at least four are OR _a ; R ₁₁ , R _14, R _15, R _18, R _19, R _22, R ₂₃ and R ₂₅ are each independently OR _a , SR _b , NR _c R _d or a halogen atom, at least one of which is NR _c R _d and at least four are OR _a ; Each of R _a , R _b , R _c and R _d independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms.

The diimmonium compound may include a diimonium compound or a derivative thereof. The derivative may include an ionic compound having the form of a salt or a substituent compound in which the hydrogen atom contained in the diimonium compound is replaced with a specific functional group. The examples of the functional groups are not limited to a wide variety, and various known functional groups or atomic groups can be used without limitation.

The diimonium compound may be a compound having a general formula represented by the following general formula (15).

[Chemical Formula 15]

In Formula 15, m is an integer of 1 or 2, and the cyclic structure B is a phenyl group coded to at least one amino group.

The content of the colorant may be 0.01 to 20 wt%, or 0.1 to 10 wt%, or 1 to 8 wt% based on the weight of the polymer beads. If the content of the colorant relative to the polymer beads is excessively reduced to less than 0.01% by weight, it is difficult to sufficiently realize the optical property to selectively absorb light in the infrared region in the polymer bead.

If the content of the coloring agent in the polymer beads is excessively increased to more than 20% by weight, a part of the coloring agent may migrate in the polymer beads, and the mechanical properties and heat resistance of the polymer beads may decrease .

The colorant may include at least one functional group selected from the group consisting of an amide group, an ester group, a vinyl group, a hydroxyl group, an acrylic group and a carboxyl group. Accordingly, the colorant increases the bonding property with the polymer resin in the polymer bead, thereby achieving excellent weather resistance and durability while preventing migration of the colorant.

More specifically, the phthalocyanine compound, the cyanine compound, and the diimonium compound or a mixture of two or more thereof may contain one kind selected from the group consisting of the amide group, the ester group, the vinyl group, the hydroxyl group, the acrylic group and the carboxyl group At least one of the above functional groups may be substituted.

The colorant may further include a perylene compound, an isoquinoline compound, an europium compound, a squarane compound, an anthraquinone compound, an acridone compound, an azo compound, a premazine compound or a mixture of two or more thereof . More specifically, metal compounds of perylene red, perylene orange, perylene yellow, benzoisoquinoline, butane dianate europium, iron oxide, CrCu or Carbon Balck, diarylide yellow, diarylide AAOT yellow And quinacridone, azo, rhodamine, perylene pigment series or colored pigment compounds of Hansa yellow G particles, and the like.

The polymer beads may include at least one polymer resin selected from the group consisting of a polyvinyl resin, a polysiloxane resin, and a polyurethane resin. By using the polymer resin, the mechanical properties and heat resistance of the polymer bead can be secured, and the cost of the product can be relatively low, thereby ensuring economical efficiency in production of the product.

When a polystyrene resin or the like having a benzene ring structure is used as in conventional bead particles, the problem of yellowing due to the double bond of the benzene ring structure and the solvent resistance to the polar solvent are insufficient. On the other hand, the polyvinyl resin, polysiloxane resin , A polyurethane resin, or a mixture of two or more of them, there is an advantage that not only the solvent resistance is improved while preventing yellowing, but also the dispersibility in an aqueous solvent is excellent and transparency can be secured.

The polyvinyl resin may include a (meth) acrylate-based repeating unit. The (meth) acrylate-based repeating unit means a repeating unit derived from a homopolymer of a (meth) acrylate-based monomer, that is, a repeating unit derived from a (meth) acrylate-based monomer.

Examples of the (meth) acrylate monomer include, but are not limited to, monofunctional (meth) acrylate compounds having 1 to 20 carbon atoms, monofunctional fluoro (meth) acrylate compounds having 1 to 20 carbon atoms, A polyfunctional (meth) acrylate compound or a mixture of two or more thereof.

The term "monofunctional (meth) acrylate compound" means a case where one (meth) acrylate functional group contained in the (meth) acrylate compound is one, and " (Meth) acrylate functional group contained in the < RTI ID = 0.0 > compound. ≪ / RTI >

Examples of the monofunctional (meth) acrylate compound having a carbon number of 1 to 20 are not limited to a great degree, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ) Acrylate, or a mixture of two or more thereof.

Examples of the monofunctional fluoro (meth) acrylate compound having 1 to 20 carbon atoms include fluoromethyl (meth) acrylate, fluoroethyl (meth) acrylate, fluorobutyl (meth) And mixtures of two or more.

Examples of the polyfunctional (meth) acrylate compound include, but are not limited to, 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, divinylbenzene, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate Polypropylene glycol diacrylate, polybutylene glycol diacrylate, allyl acrylate, 1,2-ethanediol dimethacrylate, 1,3-propane diacrylate, 1,3-propane diacrylate, Diol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol Dimetak Propylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, allyl Methacrylate, trimethylol methane tetraacrylate, trimethylol methane triacrylate, trimethylol butane triacrylate, ethylene glycol dimethacrylate, or a mixture of two or more thereof.

The polysiloxane-based resin may include polyorganosilsesquioxane.

The polyorganosilsesquioxane may include a repeating unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, R ¹ to R ⁸ are each independently hydrogen or a straight or branched alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 or more.

The polyorganosilsesquioxane may be a compound having a ladder or cage structure having a weight average molecular weight of 1,000 to 200,000.

Specifically, the polyorganosilsesquioxane may include polymethylsilsesquioxane, polyethylsilsesquioxane, polypropylsilsesquioxane, polybutylsilsesquioxane, or a mixture thereof, and preferably, May be polymethylsilsesquioxane.

Examples of the method for producing the polyorganosilsesquioxane are not limited, but include, for example, methoxysilane, ethoxysilane, propyltrimethoxysilane, methyltrimethoxysilane and ethyltrimethoxysilane. A method of hydrolyzing and condensing the at least one alkoxysilane compound selected from the group consisting of the above-mentioned monomers into monomers can be used.

The polyurethane resin is a polymer having a urethane bond obtained by polymerizing a polyol and a polyisocyanate in a molecular main chain and having a hydrophilic group at a molecular end and being well dispersed in water. The polyisocyanate is an aliphatic, alicyclic, aromatic aliphatic, Or an aromatic organic diisocyanate can be used. As the polyol, a polyester polyol, a polyether polyol or other known polyol having an average molecular weight of 500 to 5000 can be used.

The method for producing the polymer bead includes at least one monomer selected from the group consisting of a (meth) acrylate compound, an alkoxysilane compound, a polyisocyanate compound, and a polyol compound, a colorant having a maximum light absorption wavelength at a wavelength of 700 nm or more, And suspending and polymerizing the reaction solution containing the initiator.

The colorant may have a solubility in the monomer of 50% or more, or 50% to 100%. As such, the colorant can have a high solubility with respect to the monomer, so that it can be dissolved in the monomer in the reaction solution to realize excellent optical characteristics and durability.

If the solubility of the colorant in the monomer is less than 50%, the colorant may not be stably and uniformly dispersed in the reaction solution, and may migrate to the surface of the bead to be finally produced.

The content of the at least one monomer selected from the group consisting of the colorant, the (meth) acrylate compound, the alkoxysilane compound, the polyisocyanate compound and the polyol compound may include all of the contents described in the first embodiment have.

The initiator is a compound capable of initiating polymerization by pyrolysis on the reaction solution, and examples thereof include 2,2-azobisisobutyronitrile, 4,4-azobis (4) -cyanopentanoic acid, 2,2 Azo initiators such as azobis (2-methylbutyronitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, And peroxide compounds such as octanoyl peroxide, dicumyl peroxide and the like.

The reaction solution may further contain a suspension stabilizer, an aqueous solvent or a mixture of two or more thereof.

Examples of the suspension stabilizer include, but are not limited to, polyvinylpyrrolidone, polyvinylmethylether, polyethyleneimine, polymethylmethacrylate acrylic acid copolymer, polyvinyl alcohol, vinyl acetate copolymer, ethylcellulose, Hydroxypropylcellulose, or a mixture of two or more thereof.

The aqueous solvent may include water or a hydrophilic solvent, and preferably ion exchanged water may be used. The ion-exchanged water mainly refers to pure water purified by ion exchange. Preferably, the ion-exchanged water has a low cation content and can use ultrapure water having a resistance value of 5 M? Or more under a nitrogen stream generated through an ion exchanger.

The method of producing the polymer beads may include suspending and polymerizing the reaction solution. Examples of the suspension polymerization step are not limited, but include, for example, stirring the reaction solution to prepare a suspension; And polymerizing the suspension. The suspension means a liquid in which solid fine particles are dispersed.

Specifically, the stirring step of the reaction solution may include: a first stirring step of stirring at a speed of 500 rpm to 1,000 rpm for 20 minutes to 60 minutes; And a second stirring step of stirring for 10 minutes to 60 minutes at a speed of 5,000 rpm to 10,000 rpm.

If the stirring speed is not sufficiently high in the first stirring step of stirring the reaction solution at a speed of 500 rpm to 1,000 rpm or 600 rpm to 800 rpm for 10 minutes to 60 minutes or 20 minutes to 40 minutes, Stable particle formation may be difficult.

Although there is no particular limitation on the specific stirring method for carrying out the first stirring step, for example, there can be used a method in which the reaction solution is placed in a reactor and stirred using a mechanical stirrer.

After the first stirring step, the second stirring step may be performed at a speed of 5,000 rpm to 10,000 rpm, or 6,000 rpm to 8,000 rpm for 10 minutes to 60 minutes, or 20 minutes to 40 minutes.

If the polymerization is carried out immediately after the first stirring step without the second stirring step, a polymer bead having an extremely wide particle distribution as well as an aggregation phenomenon can be produced.

Examples of a specific stirring method for proceeding the second stirring step are not limited to a specific method. For example, a method of discharging a reaction solution through a first stirring step and stirring through a homomixer can be used .

The polymerization step of the suspension may be carried out at a temperature of 50 ° C to 90 ° C for 6 hours to 10 hours. At this time, the stirring speed should be appropriately maintained so that the polymer beads generated in the polymerization reaction do not sink. Preferably, the stirring speed may be 100 to 300 rpm.

Further, the step of polymerizing the suspension may further include filtration, washing and drying. The filtration, washing and drying methods can be used without any limitations in various methods conventionally used.

In addition, after the drying step, it may further include a pulverizing step, if necessary. Examples of the pulverizing method include a pulverizer such as a jet mill, a ball mill atomizer or a hammer mill.

According to a second embodiment of the present invention, the polymer bead of the first embodiment; And a plurality of metallic nanoparticles bonded to the surface of the polymer beads.

The polymer bead complexes bind metallic nanoparticles exhibiting an ultraviolet blocking effect of a wavelength of 290 to 400 nm on the surface of the polymer beads of the embodiment, which exhibit a near-infrared ray blocking effect at a wavelength of 750 nm to 1000 nm, thereby simultaneously shielding near infrared rays and ultraviolet rays Optical characteristics can be realized.

The metal nanoparticles are fine particles which remain adsorbed when exposed to the skin and may have harmful effects on the human body. However, in the polymer bead composite, the metallic nanoparticles may be physically attached to the surface of the polymer beads, The binding of the metallic nanoparticles to the metal nanoparticles can be prevented.

In addition, the polymer bead complex can uniformly bind the metallic nanoparticles to the surface of the polymer bead, sufficiently realize high refractive index by the metallic nanoparticles, maintain a uniform spherical shape, And can be stably dispersed.

The content of the polymer beads may include the above-described contents of the first embodiment.

The polymer bead complex may include a plurality of metallic nanoparticles bonded to the surface of the polymer bead. The metallic nanoparticles mean nano-sized particles containing a semi-metallic substance having a property of metal or metal.

The metallic nanoparticles may have a particle diameter of 1 nm to 500 nm, or 2 to 400 nm, or 10 to 300 nm, or 20 to 200 nm. The particle size of the metallic nanoparticles may be based on the primary particle.

The particle diameter of the metallic nanoparticles may be 1 nm or more in terms of cost and dispersion, and may be 500 nm or less in terms of surface property control. Particularly, when the particle size of the metallic nanoparticles exceeds 500 nm, the metallic nanoparticles form a concavo-convex structure on the surface of the polymer nanoparticles when they are bonded to the surface of the polymer bead.

 The metallic nanoparticles may include at least one selected from the group consisting of metal oxides and metal salt compounds. The metal oxide refers to a compound in which a semi-metallic substance having a property of a metal or a metal is chemically bonded with oxygen, and the metal salt compound means an ionic compound in which a metal is contained in the form of a cation.

The metal contained in the metal oxide may include a transition metal, and examples of the transition metal include titanium (Ti) and zinc (Zn). An example of a semi-metallic material having a property of a metal contained in the metal oxide is antimony (Sb). More specifically, examples of the metal oxide include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), antimony oxide (Sb ₂ O ₃ ), and the like.

The metal salt may include an inorganic acid salt of a metal. The inorganic acid salt of the metal is a reaction product produced through a reaction between a metal and an inorganic acid, and the inorganic acid salt of the metal may include a sulfate, a nitrate, a halogenate, a carbonate and the like of a metal. More specifically, For example, barium sulfate (BaSO ₄ ).

The metallic nanoparticles may include titanium oxide having a rutile type crystal structure. The polymer bead composite of the second embodiment ensures a high refractive index, satisfies the solvent resistance in the liquid bath system, and improves the dispersibility in the manufacture of compounding, so that the polymer bead composite can be coated It is desirable that the nano-sized metallic particles maintain high refractive index characteristics.

In order to satisfy such a high refractive index characteristic, the metallic nanoparticles may have a rutile type crystal structure, and preferably a rutile type titanium oxide (TiO ₂ ) Can be used.

Specifically, the titanium oxide (TiO ₂ ) is classified into anatase, rutile, and brookite according to the structure, but titanium oxide (TiO ₂ ) in the form of rutile Stability at a high temperature and a high refractive index can be realized.

The titanium oxide may further include a surface modification layer formed on the surface of the titanium oxide and including silicon oxide and aluminum oxide. The titanium oxide may improve the hydrophilicity of the titanium oxide by dispersing and coating a nanomineral including silicon oxide (SiO ₂ ) and aluminum oxide (Al ₂ O ₃ ) on the surface to form a surface modification layer.

When the hydrophilicity of the titanium oxide is increased, the physical adsorption property with the polymer beads increases, and the binding force between the polymer beads and the metallic nanoparticles in the polymer bead complex can be improved.

The polymer bead complex may include 0.1 to 60 parts by weight of metallic nanoparticles relative to 100 parts by weight of polymer beads. If the content of the metallic nanoparticles is less than 0.1 part by weight relative to 100 parts by weight of the polymer beads, it may be difficult to realize the high refractive index effect of the metallic nanoparticles. If the content of the metallic nanoparticles is excessively increased to more than 60 parts by weight with respect to 100 parts by weight of the polymer beads, the metallic nanoparticles may aggregate in excess of the surface area of the polymer beads, The characteristics may be degraded.

Specifically, 70 to 98 parts by weight, or 75 to 95 parts by weight, or 80 to 90 parts by weight of the polymer beads may be used based on 100 parts by weight of the total weight of the polymer bead composite. Also, 2 to 30 parts by weight, or 5 to 25 parts by weight, or 10 to 20 parts by weight of metallic nanoparticles may be used relative to the total weight of 100 parts by weight of the polymer composite powder.

Examples of the shape of the polymer bead composite are not limited to a wide range. For example, the polymer bead composite may have a spherical shape, a spherical shape, a polyhedral shape, and the cross section of the polymer bead composite may be circular, elliptical, or polygonal of 3 to 50. The polymer bead composite may have a particle size of 1 탆 to 500 탆, or 2 탆 to 400 탆, or 2 탆 to 300 탆, or 2 탆 to 50 탆. If the particle diameter of the polymer bead complex is excessively increased to more than 500 탆, the optical efficiency of the polymer bead composite may decrease.

The polymer bead composite may have a coefficient of variation of 1% to 30%, or 5% to 25%, obtained by the following formula (1). Accordingly, the polymer bead complex can maintain a spherical shape with a uniform size, and can prevent the decrease of the electrooptic properties due to diffuse reflection of the metallic nanoparticles contained in the polymer bead composite.

[Equation 1]

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

The polymer bead complex has a yield of 90% or more, or 93% or more, or 95% or more, and the manufacturing process is very effective, and the stability of the liquid preparation is excellent and the yellowing problem is controlled.

The SPF ultraviolet barrier index of the polymer bead complex may be 10 or more. The SPF index indicates the degree of blocking ultraviolet B (UVB) having a wavelength of 290 to 320 nm. The larger the SPF index value, the higher the blocking effect. Specifically, the SPF index is a value obtained by dividing the minimum erythema amount of the skin applied with the sunscreen (the minimum amount of ultraviolet ray (MED) that causes reddish erythema (MED) to the minimum erythema amount of the skin .

The polymer bead complex has a high SPF ultraviolet barrier index of 10 or more and can prevent skin aging such as wrinkles caused by ultraviolet rays, pigmentation such as freckles, elastic loss, skin cancer and the like.

In addition, the polymer bead composite may be prepared by binding metallic nanoparticles exhibiting an ultraviolet blocking effect of a wavelength of 290 to 400 nm to the surface of the polymer bead of the embodiment, which exhibits a near-infrared ray blocking effect at a wavelength of 750 nm to 1000 nm, It is possible to realize an optical characteristic for blocking at the same time.

Specifically, the polymer bead conjugate may have an absorption peak at a wavelength of 350 nm or less and an absorption peak at a wavelength of 800 nm or more, respectively. The absorption peak means an inflection point where the differential value of the absorbance with respect to wavelength changes from positive to negative as the wavelength increases. In addition, the polymer bead composite may have a light absorption coefficient at a wavelength of 350 nm or less and a light absorption rate at a wavelength of 800 nm or more of 20% or more, respectively. The light absorption rate means a ratio of the actually measured absorbance to the measurable maximum absorbance, and the maximum measurable absorbance is 2.0.

Examples of the method of preparing the polymer bead complex may include, but are not limited to, binding the metallic nanoparticles to the surface of the polymer bead prepared in the first embodiment. The step of binding the metallic nanoparticles to the surface of the polymer beads may be performed by mixing the polymer beads with the metallic nanoparticles and using a dry coating method using mechanofusion.

 The above-mentioned mechanofusion can physically chemically bond between the polymer beads and the metallic nanoparticles, so that the nanoparticles can be coated directly on the surface of the polymer beads, . The equipment used for such a dry surface coating is Nobilta NOB-130 from Hosokawa, Japan using mechanofusion principle.

An example of the dry coating method using the mechanofusion will be described in detail with reference to FIG. The polymer beads and metallic nanoparticles prepared in the first embodiment are placed in the inner container (A) of the dry high energy type mixer (B). Thereafter, the inner vessel A is rotated to collect the polymer beads and the metallic nanoparticles toward the inner wall of the inner vessel A by centrifugal force, and the inner wall of the inner vessel A and the armature D The polymer beads and the metallic nanoparticles are passed through the space of the polymer beads and the metallic nanoparticles to apply a strong shearing force and compressive force to the polymer beads and the metallic nanoparticles. Thereby, sufficient heat energy is generated between the polymer beads and the metallic nanoparticles to cause mechanofusion, resulting in strong physico-chemical bonding between the polymer beads and the metallic nanoparticles.

The scraper C is disposed on the inner wall of the inner container A among the polymer particles and the inorganic powder nanoparticles which have passed between the inner container A and the armor D by physical compression Scrape the attached materials and help them participate in the mechano-fusion reaction.

The process time of the dry coating method using the mechanofusion can be controlled from 1 minute to several hours, or from 5 minutes to 60 minutes, or from 10 minutes to 30 minutes, and the structure control of the polymer bead composite thus prepared Is possible.

Further, the rotation speed of the inner container (A) may be 500 rpm to 5,000 rpm, or 1,000 rpm to 4,000 rpm, or 1,500 rpm to 3,500 rpm. Since the intensity of the physical force received by the polymer beads and the metallic nanoparticles is controlled according to the rotation speed of the inner container, the shape and structure of the polymer bead complex can be controlled through controlling the rotation speed.

The clearance between the inner wall of the inner container (A) and the armor (D) may be 0.1 mm to 3 mm, or 0.5 mm to 2 mm, or 1 mm to 1.5 mm. The size of the gap between the inner wall of the inner container A and the armor D can control the shape of the polymer bead composite, which affects the number of collisions.

The treatment atmosphere of the dry coating method using the mechanofusion can be controlled by air, nitrogen or argon.

According to a third aspect of the present invention, there is provided an optical particle composition comprising at least one selected from the group consisting of the polymer beads of the first embodiment and the polymer bead complex of the second embodiment. That is, the optical particle composition may include the polymer beads of the first embodiment, the polymer bead conjugates of the second embodiment, or a mixture thereof.

The polymer beads of the first embodiment and the polymer bead composites of the second embodiment can have optical properties such as near infrared ray shielding property or ultraviolet shielding property, respectively, which can be realized in the optical particle composition as they are, Can be applied to various applications where it is required.

Specifically, for example, the optical particle composition of the third embodiment can be used as an optical material capable of controlling optical characteristics such as a diffusion film of a TFT-LCD, a light diffusing agent of a light diffusing plate, .

In the optical particle composition, the polymer beads of the first embodiment and the polymer bead complex of the second embodiment may respectively retain the shape of the particles, and some of the polymer beads may exist in a state where the shape of the particles is broken.

The content of the polymer bead includes the contents described above with respect to the first embodiment, and the content of the polymer bead composite may include the contents described above with respect to the second embodiment.

The optical particle composition may further comprise a binder resin or a solvent, and the polymer bead of the first embodiment and the polymer bead complex of the second embodiment may be dispersed in the binder resin or the organic solvent.

Examples of the binder resin are not particularly limited, and examples thereof include poly (meth) acrylate, polystyrene, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, polyvinyl chloride and the like.

The solvent can be used without limitation as long as it is known to be usable in the production of an optical material, and both an aqueous solvent and an organic solvent 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 refers to pure water purified by ion exchange. Preferably, the ion-exchanged water has a low cation content and can use ultrapure water having a resistance value of 5 M? Or more under a nitrogen stream generated through an ion exchanger.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers (cellosolve) such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Acetic acid esters such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate and dipropylene glycol monomethyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and carbitol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; And amides such as dimethylacetamide (DMAc) and dimethylformamide (DMF). These solvents may be used alone or as a mixture of two or more thereof.

The optical particle composition may further contain various organic or inorganic additives for improving physical properties such as optical properties. The specific examples of the additive are not limited, and various additives commonly used in the field of resin compositions for optical use can be used without limitation.

On the other hand, according to the fourth embodiment of the invention, a cosmetic comprising the optical particle composition of the third embodiment can be provided. Since the cosmetic composition includes the optical particle composition of the third embodiment, the optical properties of the optical particle composition, for example, the near-infrared ray shielding property or the ultraviolet shielding property, can be implemented in the cosmetic as it is. The effect can be improved compared to the past.

In addition, the polymer beads of the first embodiment and the polymer bead composites of the optical composition of the third embodiment may provide hiding power because they have different refractive indices from those of conventional resins, and the shape of fine spherical particles So that it is possible not only to impart durability and durability to cosmetics but also to exhibit high dispersibility in water-based solvents.

The content of the optical particle composition may include the above-described contents of the third embodiment.

 Examples of the form of the cosmetic composition are not particularly limited, but may be, for example, solid, liquid, wax, gel or cream.

The cosmetics may also be used in the cosmetics field such as, for example, water, preservatives, coloring agents, dyes with coloring effect, thickeners, perfumes, alcohols, polyols, esters, electrolytes, gel formers, silicone oils, Coagulant, emulsifier, stabilizer, and the like, and a carrier. In addition, the cosmetic may further comprise, for example, cosmetic active agents such as organic and inorganic sunscreen agents, moisturizing agents, enzymes and other plant activators.

According to the present invention, it is possible to simultaneously absorb and selectively absorb light of a polymer bead, a near-infrared ray region, and an ultraviolet ray region, which are uniform in particle shape and size, excellent in mechanical properties and heat resistance, and have optical properties that selectively absorb light in the near- , An optical particle composition using the polymer bead complex, and cosmetics can be provided.

Fig. 1 shows the absorption spectra of the polymer beads obtained in Examples 1 to 3. Fig.
Fig. 2 shows a surface FE-SEM image of the polymer bead complexes obtained in Examples 5 to 8. Fig.
Fig. 3 shows the absorption spectra of the polymer bead complexes obtained in Examples 5 to 8 and Comparative Examples 2 to 3. Fig.
Fig. 4 shows a schematic structure of a dry high energy type mixer used in Examples 5 to 8. Fig.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Example  1 to 4, Comparative Example 1 : Polymer Bead  Manufacturing>

Example 1

(A), 542.786 g of ion-exchanged water, 214.02 g of methyl methacrylate (MMA), 4.3 g of 1,6-hexanediol diacrylate, 2.0 g of azobisisobutyronitrile, and 2.46 g of PND-1 dye Weight%) were mixed, placed in a reactor, and stirred at a speed of 700 rpm for 30 minutes. Thereafter, the mixture was discharged from the reactor and strongly stirred in a homomixer at a speed of 7,000 rpm for 20 minutes. The suspension prepared by the strong stirring was introduced into a 2 L reactor and heated at 60 ° C. for 7 hours while stirring at 250 rpm at a rate of 250 rpm under a nitrogen stream. The solid was filtered from the suspension, , Dehydrated, and vacuum-dried at 70 DEG C for 24 hours to prepare polymer beads.

Example 2

Polymer beads were prepared in the same manner as in Example 1 except that 4.92 g (1 wt%) of PND-1 dye (manufactured by ICB) was used.

Example 3

Polymer beads were prepared in the same manner as in Example 1 except that 9.84 g (2% by weight) of PND-1 dye (manufactured by ICB) was used.

Example 4

A polymer bead was prepared in the same manner as in Example 1 except that methyl trimethoxysilane was used in place of methyl methacrylate (MMA).

Comparative Example 1

Polymer beads were prepared in the same manner as in Example 1 except that PND-1 dye (manufactured by ICB) was not used.

< Example  5 to 8, Comparative Example  2 to 4: Polymer Bead  &Lt; / RTI &gt;

Example 5

50 parts by weight of the polymer beads prepared in Example 1 and 50 parts by weight of TiO ₂ particles having a particle size of 150 nm were charged into a dry high energy type mixer (Hybridization KOLON). At this time, NT105A (hydrophilic) product of Jiangsu Hehai Nano Science & Technology Co., Ltd. was used as the TiO ₂ particles.

Thereafter, the gap of the dry high energy type mixer was fixed at 1.0 mm, and Mechnofusion was carried out for 5 minutes at an internal vessel rotation speed of 4,000 rpm to prepare the TiO ₂ To prepare a polymer bead complex having particles bound thereto.

Example 6

A polymer bead complex was prepared in the same manner as in Example 5, except that NT105B (hydrophobic) product of Jiangsu Hehai Nano Science & Technology Co., Ltd. was used as TiO ₂ particles.

Example 7

Polymer bead complexes were prepared in the same manner as in Example 5 except that 70 parts by weight of the polymer beads prepared in Example 1 and 30 parts by weight of TiO ₂ particles having a particle size of 150 nm were added.

Example 8

70 parts by weight of the polymer beads prepared in Example 4 and 30 parts by weight of TiO ₂ particles having a particle diameter of 150 nm were charged in the same manner as in Example 1 except that the polymer beads prepared in Example 4 were used in place of the polymer beads prepared in Example 1, a _second particle Jiangsu Hehai Nano Science & Technology Co., Ltd used to prepare a polymer composite beads in the same way, and in the example 5, except using the product NT105B (hydrophobic).

Comparative Example 2

A polymer bead complex was prepared in the same manner as in Example 5, except that the polymer bead prepared in Comparative Example 1 was used instead of the polymer bead prepared in Example 1 above.

Comparative Example 3

A polymer bead complex was prepared in the same manner as in Example 6, except that the polymer bead prepared in Comparative Example 1 was used instead of the polymer bead prepared in Example 1.

< Experimental Example  : Example  And In the comparative example  Obtained Polymer Bead , Polymer Bead  Measurement of physical properties of composites>

The physical properties of the polymer beads and polymer bead composites obtained in the above 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 diameter  And coefficient of variation ( C.V .: Coefficient of variation )

The average particle size and the coefficient of variation of the polymer beads obtained in Examples 1 to 3 were measured using a particle size distribution analyzer (Coulter Electronics, Multisizer 3). The results are shown in Table 1 below. The coefficient of variation (C.V) was obtained by the following equation (1).

[Equation 1]

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

Experimental Example 2  : Solubility of dye ( % )

The dyes were dissolved in the raw materials in Examples 1 to 3, and then all of the raw materials were volatilized and the mass of the remaining dyes was determined. The solubility of the dye was measured by the mass ratio of the remaining dye to the mass of the original dye, and the results are shown in Table 1 below.

 Results of Experimental Examples 1 and 2 division Raw material dyes Dye content Average particle diameter C.V yield Solubility of dye Example 1 MMA PND-1 0.5 wt% 5.2 탆 38% 95% 100% Example 2 MMA PND-1 1 wt% 4.8 탆 42% 90% 85% Example 3 MMA PND-1 2 wt% 4.7 탆 40% 70% 52%

As shown in Table 1, the polymer beads prepared in Examples 1 to 3 are beads having an average particle diameter of 4 탆 to 6 탆, and have a particle size distribution having a coefficient of variation (CV) of 38% to 42% I could.

On the other hand, in the polymer beads of Examples 1 to 3, as the dye content was lowered from 2 wt% to 0.5 wt%, a higher yield was obtained, and the solubility of the dye was also increased.

Experimental Example 3  : Absorbance

The polymer beads obtained in Examples 1 to 3 were mixed in a DMSO solvent, and the absorbance was measured using an absorbance meter (UV-Vis Spectroscopy, EVOLUTION 600, Thermo Fisher Scientific Co.). The results are shown in Figs. 2. At this time, the content of the polymer beads in the whole mixture was 0.01%.

As a result of Experimental Example 3 (maximum absorbance measurable is 2.0) division Maximum absorption wavelength (nm) Maximum absorbance Example 1 826 1.16 Example 2 826 0.94 Example 3 826 0.474 Reference Example 1 826 1.3

Reference Example 1: Measurement of absorbance only for PND-1 dye

As shown in Table 2, it was confirmed that the polymer beads of Examples 1 to 3 including the PND-1 dye had the same maximum absorption wavelength value as in Reference Example 1, which was measured only for the pure PND-1 dye . Thus, it was confirmed that the polymeric beads containing the PND-1 dye can realize the optical characteristics of the PND-1 dye as it is.

Experimental Example 4  : Surface structure

The surface structures of the polymer bead composites obtained in Examples 5 to 8 were observed through FE-SEM, and the results are shown in Fig. 2, SEM images of the polymer bead complexes obtained in Examples 5, 6, 7 and 8 are shown as (a), (b), (c) and (d), respectively.

Carrying is also shown in 2 (a) Example 5 For the polymer bead composites of, carried out using a surface hydrophilic TIO ₂ particles NT105A, used to view (b) the surface is hydrophobic TIO ₂ particles NT105B shown in Example 6 It was confirmed that the polymeric bead composite was superior in surface adhesion.

To it it was confirmed that Figure 2 (c) For polymer beads complex of Example 7 shown in, to reduce the content of the TIO ₂ particles decreased the TIO ₂ particles bonded to the surface of the polymer beads.

Experimental Example 5 : UV protection property

In order to confirm the ultraviolet blocking effect of the polymer bead complexes obtained in Examples 5 to 8 and Comparative Examples 2 to 3, SPF (Sun Protection Factor) and PFA (Protection Factor of PFA) were measured using an SPF- 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 320 nm. The larger the SPF index value, the higher the blocking effect. Specifically, the SPF index is a value obtained by dividing the minimum erythema amount of the skin applied with the sunscreen (the minimum amount of ultraviolet ray (MED) that causes reddish erythema (MED) to the minimum erythema amount of the skin .

The PFA index indicates the degree of blocking ultraviolet A (UVA) having a wavelength of 320 to 400 nm. The larger the PFA index value, the higher the blocking effect. Specifically, the PFA index is a value obtained by dividing the value of the minimum sustained immediate blackening amount (minimum ultraviolet irradiation dose, MPPD) of the skin applied with the ultraviolet screening agent divided by the minimum sustained immediate blackening amount of the skin applied with the ultraviolet screening agent do.

 Results of Experimental Example 5 division Bead TiO2 particles Content of TiO2 particles SPF PFA Example 5 Example 1 NT105A 50 wt% 26.26 30.18 Example 6 Example 1 NT105B 50 wt% 25.12 29.25 Example 7 Example 1 NT105A 30 wt% 12.03 13.62 Example 8 Example 4 NT105B 30 wt% 12.02 13.06 Comparative Example 2 Comparative Example 1 NT105A 50 wt% 24.38 29.01 Comparative Example 3 Comparative Example 1 NT105B 50 wt% 23.42 29.35 Reference Example 2 Example 1 - - 6.2 8

- Reference Example 2: Measuring only the polymer beads prepared in Example 1

As shown in Table 3, in Examples 5 to 8 in which TIO ₂ particles were bonded to the bead surface, both the SPF index and the PFA index were higher than in Reference Example 2 in which no TIO ₂ particles were used, I can confirm that it is improved.

Further, in Examples 5 and 6, in which the content of TIO ₂ particles was high, the SPF index and the PFA index were both higher than those of Examples 7 and 8 in which the content of TIO ₂ particles was relatively small, . Comparing Example 5 and Example 6, the SPF index and the PFA index of Example 5 using NT105A as the hydrophilic TIO ₂ particle were higher than those of Example 6 using the NT105B hydrophobic TIO ₂ particle, It was confirmed that the blocking effect was improved.

Experimental Example 6 : Near infrared  Blocking characteristic

(UV-Vis Spectroscopy, EVOLUTION 600, manufactured by Thermo Fisher Scientific Co., Ltd.) was used to confirm the blocking effect of near infrared rays (wavelength of 760 to 1000 nm) of the polymer bead conjugates obtained in Examples 5 to 8 and Comparative Examples 2 to 3. [ , And the results are shown in Fig.

In the case of Comparative Examples 2 and 3, as shown in Table 3 and FIG. 3, high SPF index and PFA index were exhibited through absorption of light in the ultraviolet region, while the light absorption in the near infrared region was small and the near- It can be confirmed that it is not implemented.

On the other hand, in Examples 5 to 8, as shown in Table 3 and FIG. 3, high SPF index and PFA index were shown through absorption of light in the ultraviolet ray region, and high absorption of light was also observed in the near- At the same time.

A: Internal container
B: Dry high energy type mixer
C: Scraper
D: Armor

Claims (22)

At least one polymer resin selected from the group consisting of a polyvinyl resin, a polysiloxane resin and a polyurethane resin; And
And a colorant bonded to the polymer resin,
A polymer bead having a maximum optical absorption wavelength at a wavelength of 700 nm or greater.
The method according to claim 1,
Wherein the polymer bead has a light absorptivity of 10% or less at a wavelength of 450 nm to 650 nm.
The method according to claim 1,
Wherein the colorant has a maximum optical absorption wavelength at a wavelength of 750 nm to 1000 nm.
The method according to claim 1,
Wherein the colorant comprises at least one selected from the group consisting of a phthalocyanine compound, a cyanine compound, an anthraquinone compound, a dithiol compound, and a diimonium compound.
5. The method of claim 4,
The phthalocyanine compound includes at least one selected from the group consisting of a phthalocyanine compound, a naphthalocyanine compound, a metal-phthalocyanine complex, a metal-naphthalocyanine complex, and derivatives thereof.
The method according to claim 1,
Wherein the colorant is a vanadium phthalocyanine compound.
The method according to claim 1,
Wherein the content of the colorant based on the weight of the polymer beads is 0.01 wt% to 20 wt%.
The method according to claim 1,
Wherein the polyvinyl resin comprises a (meth) acrylate-based repeating unit.
The method according to claim 1,
Wherein the polysiloxane-based resin comprises polyorganosilsesquioxane.
The method according to claim 1,
Wherein the polymer beads have an average particle diameter of 1 占 퐉 to 500 占 퐉.
The method according to claim 1,
Wherein a coefficient of variation of the polymer beads obtained by the following formula (1) is 20% to 50%: polymer beads:
[Equation 1]
Coefficient of variation (%) = (standard deviation of polymer bead diameter / average particle diameter of polymer bead) X 100.
The polymer bead of claim 1; And
And a plurality of metallic nanoparticles bonded to the surface of the polymer beads.
13. The method of claim 12,
Wherein the metal nanoparticles have a particle diameter of 1 nm to 500 nm.
13. The method of claim 12,
Wherein the metallic nanoparticles comprise at least one member selected from the group consisting of metal oxides and metal salt compounds.
13. The method of claim 12,
Wherein the metallic nanoparticles comprise a titanium oxide having a rutile type crystal structure.
16. The method of claim 15,
Wherein the titanium oxide further comprises a surface modification layer formed on the surface of the titanium oxide and including silicon oxide and aluminum oxide.
13. The method of claim 12,
Wherein the polymer bead complex comprises 0.1 to 60 parts by weight of metallic nanoparticles relative to 100 parts by weight of the polymer bead.
13. The method of claim 12,
Wherein the polymer bead complex has an average particle diameter of 1 占 퐉 to 500 占 퐉.
13. The method of claim 12,
Wherein the coefficient of variation of the polymer bead composite obtained by the following formula (1) is 10% to 30%: polymer bead composite:
[Equation 1]
Coefficient of variation (%) = (standard deviation of polymer bead composite diameter / average particle diameter of polymer bead composite) X 100.
13. The method of claim 12,
Wherein the polymer bead complex has an SPF ultraviolet barrier index of 10 or more.
The polymer bead of claim 1, and the polymer bead complex of claim 12.
22. The cosmetic, comprising the optical particle composition of claim 21.

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