KR102194600B1 - Size-selective Polymer-inorganic Composite Particles for Blocking Near-infrared Light, and Method for Preparing the Same - Google Patents

Abstract

In the present disclosure, the near-infrared blocking effect is increased by including inorganic particles having a near-infrared blocking and/or ultraviolet blocking function in the polymer particle matrix having a predetermined size (diameter in the case of spherical particles) capable of blocking near-infrared rays, and/or Alternatively, a polymer-inorganic composite particle capable of blocking ultraviolet and near-infrared rays at the same time and a manufacturing method thereof are described.

Description

Size-selective Polymer-inorganic Composite Particles for Blocking Near-infrared Light, and Method for Preparing the Same}

The present disclosure relates to a size-selective polymer-inorganic composite particle for near-infrared blocking or simultaneous blocking of near-infrared and ultraviolet rays and a method for preparing the same. More specifically, the present disclosure increases the near-infrared blocking effect by including inorganic particles having a near-infrared blocking and/or ultraviolet blocking function in a polymer particle matrix having a predetermined size capable of blocking near-infrared rays, and/or ultraviolet and It relates to a polymer-inorganic composite particle capable of blocking near-infrared rays at the same time and a method for manufacturing the same.

Skin aging can be classified into intrinsic aging, which inevitably appears with the progress of the years, and photoaging that occurs when the skin of the face, the back of the hand, and the back of the neck is exposed to sunlight.

The sunlight reaching from the sun to the earth's surface consists of 5% of ultraviolet light, 40-45% of visible light, and 45-50% of infrared light. It is known that light aging is mainly due to ultraviolet (wavelength: 280-400 nm), and when the skin is exposed to ultraviolet rays, it accelerates skin aging, and causes local pigmentation such as freckles and age spots, and more Furthermore, it causes skin irritation and damage such as erythema and skin cancer.

On the other hand, in recent years, research on the effect of near-infrared rays and ultraviolet rays on the skin has been actively conducted. According to the results of research by Professor Jean Krutmann of Heinrich-Heine Medical University, UV-A (corresponding to the wavelength range of 320-400 nm) induces mass deletion of mtDNA from keratinocytes in the stratum corneum or fibroblasts in the dermal layer. While generating MMPs to cause photoaging, 65% of near infrared (wavelength band: 750-1,440 ㎚) penetrates deep into the subcutaneous tissue of the skin and transfers electrons from mitochondria, which are related to the formation of'active oxygen'. It has been explained that it causes skin damage, such as increasing free radicals in cells by disrupting the system and changing the collagen balance (P. Schroeder et al., Exp. Gerontology, 43, 629-632, 2008, P. Schroeder et al., J. Invest. Dermatology, 128, 2491-2497, 2008, J. Krutmann, and P. Schroeder, J. Invest. Dermatology, 14, 44-49, 2009, C. Calles, et al. , J. Invest.Dermatology, 130, 1524-1536, 2010.).

In addition, near-infrared rays are known to cause skin aging by affecting the increase in MMP-1 production and decrease in collagen. This is because ultraviolet rays directly induce mass deletion of fibroblasts to produce MMPs, while near-infrared rays stimulate mitochondria to generate free radicals and thereby undergo another process, such as generation of MMPs, but not only ultraviolet rays but also near-infrared rays are light. This is because it affects aging.

Therefore, when photoaging begins by near-infrared irradiation, the production of MMP-1 in the dermal layer in the skin increases, and as a result, it is expected that type-I and type-III collagen are decomposed and decreased. In the case of sunlight reaching the surface from the sun, considering that ultraviolet rays are about 5% and infrared rays are about 45 to 50%, research on a way to protect skin from infrared rays, especially near infrared rays, is urgently needed.

Currently, research on various near-infrared blocking materials is in progress, and in the case of infrared blocking coating films for vehicles, ITO (Indium tin oxide) is mixed with silica and used (ACS Applied Materials and Interfaces 2013, 5, 10240-10245). . However, in the case of indium compounds, there is a limit that cannot be applied to biomaterials including cosmetics due to human safety problems.

As a technology related to cosmetics that can block near-infrared rays by being applied to existing cosmetics, research has been conducted to secure the near-infrared blocking effect by mixing inorganic nanoparticles of various metal oxide materials with UV blocking ability (Korean Patent Publication No. 2011-56253, etc.). In addition, a method of manufacturing composite inorganic particles capable of simultaneously blocking near-infrared and ultraviolet rays by chemically bonding inorganic nanoparticles of metal oxide material showing ultraviolet ray blocking ability on inorganic particles made of metal oxide material having near-infrared ray blocking ability was also developed. Bar (Korean Patent Publication No. 2011-10553). In addition, there has also been reported an example in which particles coated with a silica-based inorganic compound on the surface of zirconia (ZrO ₂ ) particles having near-infrared blocking ability can be applied to cosmetics (Korean Patent Publication No. 2014-95736).

However, since most inorganic metal oxide particles exhibit a high refractive index, light is blocked by inducing high refraction of light on the surface of the particles. Therefore, in order for these particles to be effectively applied to light blocking in the near-infrared and visible light regions, a very high concentration of inorganic particles must be contained in cosmetics. In this case, a cloudiness of the skin occurs, and in the case of some metal oxide particles, photocatalytic reaction Phenomenon that can cause various side effects such as, etc.

Due to not only the technical limitations described above, but also economical and other various reasons, not only relying on the function of inorganic particles with excellent light blocking ability in the near infrared region applicable to cosmetics, but also maximizing the near infrared ray blocking ability while minimizing the use of functional inorganic particles. It is desirable to develop composite particles capable of. Furthermore, as described above, skin damage caused by exposure to ultraviolet rays is also very important, so developing polymer-inorganic composite particles that can block ultraviolet rays at the same time as near infrared rays can simplify raw materials in cosmetic formulations and reduce the amount of raw materials used. Is an important consideration.

However, in the prior art, only the metal oxide inorganic composite particles that can block near-infrared and ultraviolet rays by combining inorganic nanoparticles made of metal oxide are reported (Korean Patent Publication No. 2011-10553), and ultraviolet rays and near-infrared rays are only reported. Polymer-inorganic composite particles that can block simultaneously have not been studied.

An important consideration in the development of polymer-inorganic composite particles for blocking near-infrared rays or for blocking near-infrared rays and ultraviolet rays at the same time is whether or not it is possible to secure an optimal composite particle manufacturing technology capable of maximizing near-infrared blocking capability. In the case of inorganic particles, the degree and range of reaction to light in the vicinity of visible and near-infrared rays is primarily determined by the elemental components of the inorganic particles, and the size and anisotropy of the particles constituting the particles are effective wavelengths for blocking light. Determine the range. In particular, gold (Au), silver (Ag), and aluminum (Al) induce a localized surface plasmon resonance (LSPR) phenomenon, and are known to have excellent visible and near-infrared blocking ability. The extent to which the visible and near-infrared regions can be blocked is determined according to the degree of asphericity.

On the other hand, the light blocking effect of the polymer particles in the near-infrared region, unlike inorganic particles, is mainly dependent on changes in the geometrical structure of the particles, instead of having an insignificant effect due to changes in constituents. In the case of spherical polystyrene particles, it is known that the blocking ability of the visible and near-infrared regions of the particle size increases significantly at the micrometer level (Absorption and scattering of light by small particles, Bohren, Craig F., 1983). However, it has been reported that the light blocking effect in the visible and near-infrared regions is significantly reduced in particles of a specific size or more (eg, 1 micron or less or 5 microns or more). Furthermore, in the case of poly(methyl methacrylate; PMMA), which is more commonly used as a cosmetic material than polystyrene, whether it exhibits a light blocking effect according to the same particle size in an aqueous phase (or aqueous medium) like polystyrene. Nothing has been reported yet.

On the other hand, the manufacturing and control technology of polymer microparticles capable of having a specific size range has been reported in several literatures, but a technology for preparing composite particles of polymer-inorganic compounds having a size range effective for blocking near infrared rays is not known. This is because there are many restrictions on the manufacture of particles having a specific size range due to separation and aggregation of inorganic particles that may occur during emulsion or suspension polymerization, and other various reasons. Furthermore, in the case of a single particle composed of inorganic particles and a polymer, when the difference in refractive index between the inorganic particles and the polymer is large (for example, composed of TiO ₂ and a polymer), an optimal polymer capable of blocking the near-infrared region: composition of inorganic particles Little is known about the ratio and particle size range. In addition, in order to block near-infrared rays, a technique for selectively manufacturing a polymer-inorganic composite having a specific size range is hardly known.

In the present disclosure, based on a polymer particle matrix having a size range (diameter in the case of spherical particles) adjusted to enable near-infrared blocking, a near-infrared blocking effect is increased, and/or a polymer capable of simultaneously blocking near-infrared and ultraviolet rays- It is intended to provide an inorganic composite particle and a manufacturing method thereof.

In addition, in the present disclosure, it is intended to provide a method of applying the above-described polymer-inorganic composite particles to the manufacture of cosmetics.

According to the first aspect of this disclosure,

A spherical polymer matrix having a size range adjusted to enable near-infrared blocking; And

Inorganic particles dispersed in the polymer matrix;

As a polymer-inorganic composite particle comprising a,

(i) When the inorganic particles have a near-infrared blocking function, the near-infrared blocking effect is increased, and (ii) when the inorganic particles have an ultraviolet blocking function, a polymer-inorganic composite that provides an effect of blocking both near-infrared rays and ultraviolet rays at the same time. Particles are provided.

According to the second aspect of this disclosure,

a) forming a dispersion by dispersing inorganic particles in a mixture containing a monomer compound and a crosslinking agent;

b) adding an initiator to the dispersion; And

c) forming an emulsion by contacting the dispersion to which the initiator is added with an aqueous solution containing a combination of a polymer stabilizer and a surfactant;

As a method for producing a polymer-inorganic composite particle comprising a,

The polymer-inorganic composite particles include a spherical polymer matrix having a size range adjusted to enable near-infrared blocking, and inorganic particles dispersed in the polymer matrix,

(i) When the inorganic particles have a near-infrared blocking function, the near-infrared blocking effect is increased, and (ii) when the inorganic particles have an ultraviolet blocking function, a polymer-inorganic composite that provides an effect of blocking both near-infrared rays and ultraviolet rays at the same time. A method of making particles is provided.

According to an exemplary embodiment, the size of the polymer matrix may range from 1 to 3 μm, and the size of the inorganic particles may range from 10 to 1,000 nm.

According to an exemplary embodiment, the weight ratio of the polymer stabilizer: surfactant in the aqueous solution containing the combination of the polymer stabilizer and the surfactant in step c) is 1:0.1 so that the size of the polymer matrix is in the range of 1 to 3 μm. To 1.25.

According to an exemplary embodiment, the concentration of the polymer stabilizer in the aqueous solution containing the combination of the polymer stabilizer and the surfactant in step c) is in the range of 1 to 5% by weight, and the concentration of the surfactant is in the range of 0.5 to 2.5% by weight. Can be

According to an exemplary embodiment, the polymeric stabilizer in step c) may be a type having a molecular weight (M _w ) of 10,000 to 2,000,000.

According to an exemplary embodiment, the polymeric stabilizer in step c) is polyvinylalcohol (PVA), polyvinylpyrrolidone (PVP), polyvinyl acetate (PVAc), and polyacrylic acid. ) And polyethylene oxide (PEO) may be at least one selected from the group consisting of.

According to an exemplary embodiment, the surfactant in step c) is a cationic surfactant having a molecular weight (M _w ) of 100 to 1,500 and an HLB value of 5 to 40, anionic surfactant, both It may be at least one selected from the group consisting of amphoteric surfactants and non-ionic surfactants.

According to an exemplary embodiment, the surfactant in step c) is sodium dodecyl sulfate (SDS), sodium lauryl ether sulfate (SLES), ammonium lauryl sulfate; ALS), cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), myristyl trimethylammonium bromide (TTAB), and polysorbate (Polysorbate). It may be at least one.

According to the third aspect of the present disclosure, there is provided a cosmetic composition comprising the polymer-inorganic composite particles.

According to specific examples according to the present disclosure, light in the near-infrared region can be effectively blocked by controlling the particle size range of the polymer matrix effective for blocking near-infrared rays, and the near-infrared blocking ability is improved according to the characteristics of the inorganic particles dispersed in the polymer matrix. It can enhance and/or block near infrared and ultraviolet rays simultaneously. Therefore, it can be applied not only as a formulation of cosmetics for blocking near-infrared rays and/or simultaneously blocking near-infrared-ultraviolet rays, but also applied in various fields, such as that it can be applied as a material for a coating film for blocking near-infrared rays and/or simultaneously blocking near-infrared rays and ultraviolet rays in the automotive field It is expected to be advantageous in broadening the range.

1 is a diagram schematically showing a manufacturing process of a polymer-inorganic composite particle according to an embodiment;
Figure 2 is a graph showing the light blocking characteristics when the size of polymethyl methacrylate (PMMA) particles change;
3 is a polymer-inorganic composite in which aluminum hydroxide is contained in a PMMA matrix, and gold nanoparticles are coated on the surface of TiO ₂ (Au-Al(OH) ₃ -TiO ₂ ) inorganic nanoparticles according to Example 2 It is an optical micrograph under bright field and dark field for each of the particles, and the particles not containing inorganic particles as a control (PMMA Control);
4 is a polymer-inorganic composite particle in which Au-Al(OH) ₃ -TiO ₂ inorganic particles are dispersed in a PMMA matrix, and Au-Al(OH) ₃ -TiO ₂ does not contain inorganic particles. It is a graph comparing the light blocking properties of each control (PMMA particles);
5 is a SEM photograph and TEM photograph of a polymer-inorganic composite particle in which Au nanoparticles are dispersed in a PMMA matrix according to Example 3;
6 is a graph comparing the light-blocking characteristics of a polymer-inorganic composite particle in which Au nanoparticles are dispersed in a PMMA matrix, and a control (PMMA particle) not containing Au nanoparticles according to Example 3;
7A is an optical micrograph of a polymer-inorganic composite particle in which TiO ₂ (Al(OH) ₃ -TiO ₂ ) inorganic nanoparticles containing aluminum hydroxide in a PMMA matrix are dispersed according to Example 4;
7B is a graph showing light blocking characteristics when the size of the polymer-inorganic composite particles in which the inorganic particles are dispersed TiO ₂ (Al(OH) ₃ -TiO ₂ ) inorganic particles are dispersed in the PMMA matrix prepared according to Example 4 ego;
8 is a polymer-inorganic composite particle in which Al (OH) ₃ -TiO ₂ inorganic particles are dispersed in a PMMA matrix, and a control (PMMA particle) that does not contain Al (OH) ₃ -TiO ₂ inorganic particles according to Example 4 ) Is a graph comparing the light blocking characteristics;
9 is an optical micrograph of a polymer-inorganic composite particle in which TiO ₂ inorganic particles having a UV blocking function are dispersed in a PMMA matrix according to Example 5;
FIG. 10 is a comparison of the light blocking characteristics of a polymer-inorganic composite particle in which TiO ₂ inorganic particles having a UV blocking function are dispersed in a PMMA matrix, and a control group (PMMA particles) not containing TiO ₂ inorganic particles according to Example 5 One graph;
Each of FIGS. 11A and 11B shows that when PVA is used as a polymer stabilizer and polysorbate (Tween 20) is used as a surfactant, the concentration of Tween 20 is changed at a fixed PVA concentration (2% by weight). It is a graph showing the optical micrograph of the composite particle (Al(OH) ₃ -TiO ₂ @PMMA) and the light blocking characteristics (UV-VIS-NIR Spectrum) according to the size change;
12A and 12B respectively show composite particles according to varying the concentration of SDS at a fixed PVA concentration (2% by weight) when PVA is used as a polymer stabilizer and SDS is used as a surfactant (Al(OH) _3- TiO ₂ @PMMA) is an optical microscope picture;
13a and 13b, respectively, when PVA is used as a polymer stabilizer and SDS is used as a surfactant, composite particles according to changing the concentration of PVA at a fixed SDS concentration (1% by weight) (Al(OH) _3- TiO ₂ @PMMA) photomicrograph (when using an appropriate amount of PVA and when using an amount out of the appropriate amount);
14A and 14B show that in the preparation of polymer-inorganic composite particles in which Al(OH) ₃ -TiO ₂ is dispersed in a PMMA matrix, the amount of linear polymer added to the monomer mixture (Al(OH) ₃ -TiO ₂ ): monomer and linear polymer It is an optical microscope photograph showing the effect of the dispersion stability (when using an appropriate amount of linear polymer and when using an amount out of the appropriate amount) on the dispersion stability of (5% by weight relative to the total);
15A and 15B show the polymer-inorganic composite particles in which Al(OH) ₃ -TiO ₂ is dispersed in the PMMA matrix in the amount of linear polymer added (when an appropriate amount of linear polymer is used and when a linear polymer is used in an amount outside the appropriate amount) It is an optical micrograph showing the effect on the properties of; And
FIG. 16 is a cosmetic composition containing polymer-inorganic composite particles in which Au-Al(OH) ₃ -TiO ₂ inorganic particles are dispersed in a PMMA matrix, a cosmetic composition containing PMMA particles not containing inorganic particles, and light of each cosmetic formulation This is a graph comparing blocking characteristics.

The present invention can all be achieved by the following description. The following description should be understood as describing preferred embodiments of the present invention, and the present invention is not necessarily limited thereto. In addition, the accompanying drawings are intended to aid understanding, and it should be understood that the present invention is not limited thereto.

Terms used in the present specification may be defined as follows.

“Polymer” includes both homopolymers and copolymers, and copolymers can be understood to include random copolymers and block copolymers.

"Linear polymer" may mean a polymer in which a long chain is formed without a crosslinked structure of molecules in the polymer.

"Emulsion" can usually mean a stabilized mixture of at least two immiscible liquids, in some cases by the addition of a surfactant (or emulsifier) that reduces the interfacial tension between the at least two immiscible liquids. Can be stabilized.

"HLB (hydrophile-lipophile balance)" refers to an index indicating the balance of hydrophilicity and lipophilicity, and the stronger the property of the hydrophilic head group and the weaker the property of the lipophilic tail group (That is, the shorter the tail length, the higher the HLB value).

A. Polymer-inorganic composite particles

According to one embodiment of the present disclosure, the polymer-inorganic composite particle largely includes a spherical polymer matrix and inorganic particles, and specifically, an inorganic particle having near-infrared blocking ability and/or ultraviolet blocking ability in the spherical polymer matrix May be in a distributed form.

In this regard, the polymer matrix may have a predetermined size range (diameter in the case of spherical particles) to be effective in blocking near infrared rays. In the case of spherical particles, light is generally blocked by scattering or absorbing a wavelength of light corresponding to the particle size as the particle size approaches a specific wavelength of light. For example, in the case of particles composed of only a polymer matrix, light blocking properties may change depending on the size of the particles.

At this time, it should be noted that as the size of the particles increases from the nano level to the micro level, the light blocking effect increases in the visible and near infrared regions. In particular, in the case of the polymer-inorganic composite particle according to the present embodiment, it will be understood that the size of the composite particle substantially corresponds to the particle size of the polymer matrix as it may be in a form in which a plurality of inorganic particles are dispersed in the polymer matrix. In this specification, it may be used as an interchangeable expression according to the purpose of the description.

According to an exemplary embodiment, the polymer matrix may be a polymer typically prepared from radically polymerizable monomers, and more specifically may be made of a mixture of a linear polymer and a crosslinked polymer. At this time, in the case of a linear polymer, the molecular weight (M _w ) may be, for example, about 5,000 to 350,000, specifically about 20,000 to 200,000, and more specifically about 50,000 to 150,000, but this may be understood as an exemplary meaning. .

The material of such a polymer matrix is, for example, polymethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl Methacrylate, polypentyl acrylate, polypentyl methacrylate, polyglycidyl methacrylate, polycyclohexyl acrylate, poly (2-ethylhexyl acrylate), polyacrylic acid and polymethacrylic acid, polystyrene, And it may be selected from the group consisting of a copolymer thereof. More specifically, the material of the polymer matrix may be selected from the group consisting of polymethyl methacrylate, polymethyl acrylate, polyacrylic acid and polymethacrylic acid, polystyrene, and copolymers thereof. In the case of polymethyl methacrylate (PMMA), which is a material of a representative polymer matrix, it may be expressed as in General Formula 1 below.

[General Formula 1]

Here, n is an integer of about 50 to 3500 (specifically, from 200 to 2000, more specifically 500 to 1500) in the case of a linear polymer.

On the other hand, in the case of inorganic particles incorporated into the polymer matrix, (i) when it has a near-infrared blocking function, it increases the near-infrared blocking effect of the polymer matrix, and/or (ii) when it has a UV blocking function, it originates from the polymer matrix. The near-infrared blocking effect and the ultraviolet blocking effect by inorganic particles are combined to provide a near-infrared blocking-ultraviolet blocking effect at the same time.

Whether the inorganic particles can block near-infrared rays and/or ultraviolet rays can be determined primarily from the constituent elements of the particles. However, it is necessary to understand that specific inorganic particles are not limited to having only a near-infrared blocking effect or only an ultraviolet blocking effect, and can express both functions depending on how the material and size are controlled.

For example, in the case of an inorganic particle for blocking ultraviolet rays (specifically, TiO ₂ , ZnO, CeO _2, etc.), it is known to have an overall blocking ability against light in the ultraviolet region. In addition to this, the inorganic particles for UV blocking also have a high refractive index, and when their size exceeds a certain level (for example, approximately 300 nm), effective blocking of light in the visible region due to the refraction of light It can also show ability. However, in order to effectively block the visible and near-infrared regions, a large amount of inorganic particles must be added to the cosmetic formulation, and through this, when the cosmetic is applied to the skin, the inorganic particles are present in the form of a film and refract light to effectively reduce the near-infrared rays. Can be blocked. In this case, considering negative phenomena such as dispersion safety, cloudiness, and photocatalytic reaction in the cosmetic formulation that occur when a large amount of inorganic particles are added to the cosmetic, effective near-infrared rays can be effectively blocked even if a small amount is used. Introduction of inorganic particles may be desirable.

In consideration of the above, in a specific example of the present disclosure, a light blocking effect in the near-infrared region is provided by adjusting the size of the polymer matrix particles, but additionally, the near-infrared blocking effect is provided by providing a near-infrared blocking effect by inorganic particles. It enhances and/or provides a UV blocking effect to achieve simultaneous blocking of near infrared and ultraviolet rays.

According to an exemplary embodiment, the inorganic particles having a near-infrared blocking function may be based on an element exhibiting LSPR (Localized Surface Plasmon Resonance) characteristics. Inorganic particles having such a near-infrared blocking function can have an effective near-infrared blocking ability even when they have a size of a visible wavelength or less, M. E. Stewart et al., Chem. Rev. 2008, 108, 494; C. M. Cobley et al., Chem. Soc. Rev. 2011, 40, 44; ACS Nano 2014, 8, 834), etc., are described in detail, and the documents are incorporated by reference in this specification. As such, the inorganic particles having a near-infrared blocking function may include, for example, a metal element selected from the group consisting of Au, Al, and Ag.

As a specific example of the near-infrared blocking inorganic particles, Au; Al ₂ O ₃ ; Al(OH) ₃ ; Ag; TiO ₂ containing aluminum hydroxide (Al(OH) ₃ -TiO ₂ ); In addition, aluminum hydroxide may be contained, and at least one may be selected from the group consisting of TiO ₂ (Au-Al(OH) ₃ -TiO ₂ ) coated with gold nanoparticles on the surface.

On the other hand, according to an exemplary embodiment, the inorganic particles having a UV blocking function, for example, TiO ₂ , ZnO, ZnO ₂ , CuO, CuO ₂ , Al ₂ O ₃ , Al(OH) ₃ , CeO ₂ , Ce ₂ At least one may be selected from the group consisting of O ₃ , Fe ₂ O ₃ , and ZrO ₂ .

In this regard, the size of the inorganic particles (near-infrared blocking inorganic particles and ultraviolet blocking inorganic particles) may be at the nano level as a whole, for example, about 10 to 1,000 nm, specifically about 20 to 800 nm, more specifically It can be determined in consideration of the desired function, elements of inorganic particles, geometric shapes, etc. within the range of about 50 to 500 nm, and any combination is possible within the aforementioned size range. According to a specific embodiment, the size of the near-infrared blocking inorganic particles is, for example, about 20 to 1000 nm, specifically about 40 to 800 nm, more specifically in the range of about 100 to 500 nm, and The size may be determined within a range of, for example, about 100 nm or less, specifically about 10 to 90 nm, and more specifically about 20 to 80 nm.

According to one embodiment, the near-infrared blocking or ultraviolet blocking inorganic particles may be mixed with a monomer in the process of synthesizing the polymer-inorganic particles composite particles, and the inorganic particles in the resulting composite particles are contained within the polymer matrix. It can have a form that is dispersed in.

Even when a small amount of near-infrared or ultraviolet-blocking inorganic particles are used in cosmetics, etc., when aggregation is caused by a decrease in dispersion stability in a cosmetic formulation, the light blocking efficiency may be rapidly reduced. Furthermore, considering economic factors such as the case of using inorganic particles with good human safety and particle stability in an aqueous medium (e.g., expensive Au-containing inorganic particles as inorganic particles having LSPR characteristics specifically) , It may be advantageous to secure the dispersion stability of the inorganic particles in the polymer matrix, and to secure the light blocking ability as a target by appropriately adjusting the content (or amount of use) thereof.

In this regard, the degree of dispersion of the inorganic particles contained in (or dispersed) in the polymer matrix can be qualitatively measured by an optical microscope or an electron microscope, so it is advantageous to uniformly disperse while suppressing the aggregation phenomenon as much as possible.

As described above, depending on the type of inorganic particles contained in the polymer matrix, the refractive index of the composite particles is significantly affected. Unlike the case of single polymer particles, light blocking in a specific band depends on the content of inorganic particles used in the composite particles. The ability (for example, near-infrared blocking ability) may change. Therefore, it may be advantageous to control the size and content of the composite particles so that the polymer-inorganic composite particles can maximize the blocking effect for desired light (reinforcement of the near-infrared blocking effect and/or simultaneous blocking of near-infrared-ultraviolet rays). From this point of view, for the purpose of the present disclosure, the inorganic particles having a near-infrared blocking function and the inorganic particles having a UV blocking function should not be understood as distinct meanings, and a single inorganic particle may exhibit both of these functions. Or, by mixing and using each of the inorganic particles having two functions in an appropriate ratio, not only the effect of increasing the near-infrared blocking effect, but also the near-infrared-ultraviolet blocking effect may be simultaneously implemented.

In this regard, the size (or diameter) of the composite particles or polymer matrix may vary somewhat depending on the type (element, size, particle shape) of the inorganic particles to be used and the type of the polymer matrix, for example, about 1 to It may be in the range of 3 μm, specifically about 1.1 to 2.5 μm, and more specifically about 1.2 to 2 μm. In particular, according to an exemplary embodiment, the average particle size (D ₅₀ ) of the composite particles or the polymer matrix is, for example, about 1.5 to 2 μm, specifically about 1.6 to 1.9 μm, more specifically about 1.7 to 1.8 μm. It may be advantageous to adjust to be within.

If the concentration of the inorganic particles contained (dispersed) in the polymer matrix is too high, the degree of aggregation of the inorganic particles (or inorganic nanoparticles) increases, so it may be difficult to effectively exhibit the light blocking ability of the individual inorganic particles. In this regard, when the content of the inorganic particles in the polymer-inorganic composite particle is below a certain level (eg, about 10% by weight or less), the particle characteristics of the polymer matrix may mainly affect the near-infrared blocking ability. In addition, when inorganic particles exhibiting LSPR characteristics as inorganic particles, such as gold (Au) nanoparticles, are introduced into the polymer matrix, even if they are contained in small amounts (for example, as low as about 0.05% by weight), near-infrared rays are blocked. In addition to the effect, it is possible to provide an additional UV blocking effect. Therefore, compared to the case of using only the same amount of inorganic particles, the near-infrared and/or UV-blocking ability can be significantly improved.As noted above, the whitening phenomenon of cosmetics and photocatalytic reaction that can occur when a large amount of inorganic particles are mixed. It is noteworthy that undesirable phenomena such as the like can be suppressed.

In consideration of the above points, according to an exemplary embodiment, the content of the inorganic particles, based on the total weight of the polymer-inorganic composite particles, for example, about 0.05 to 10% by weight, specifically about 0.5 to 8% by weight, More specifically, it may range from 1 to 5% by weight, and any sub-combination within this numerical range is possible. However, the content range may be appropriately changed depending on the material and size of the inorganic particles used.

B. Method for producing polymer-inorganic composite particles

According to another embodiment of the present disclosure, a method for producing a polymer-inorganic particle composite particle having a function of blocking near infrared rays and/or blocking near infrared rays and ultraviolet rays simultaneously is provided. The manufacturing process of the polymer-inorganic composite particle according to an embodiment is shown in FIG. 1.

In order to prepare polymer particles having uniform size distribution characteristics as in this specific example, in general, the composition of the dispersion medium is adjusted so that the monomer can be dissolved in the dispersion medium, and the solubility of the polymer chain increases as the polymerization proceeds. A spherical seed is formed by allowing the to be lowered, and the particles are designed to grow subsequently (Chemical Engineering Journal 78 (2000) 211-215).

At this time, in the case of microparticles, in order to secure dispersion stability, a polymer dispersion stabilizer (eg, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), etc.) may be used. However, the present inventors, in the process of polymerization by mixing inorganic particles with a monomer in order to prepare composite particles of high-branched-inorganic particles, the density difference between the inorganic particles and the monomer, the dispersibility between the solvent (liquid medium) and the inorganic particles, and As polymerization proceeded, it was found that it was difficult to prepare composite particles due to the induction of aggregation of inorganic particles due to the generation of polymers.

As an alternative to this, it is possible to propose a method of performing polymerization while inducing the inorganic particles to maintain dispersibility in the monomer through an emulsion method. However, as in this embodiment, in order to synthesize composite particles having a predetermined size range effective for blocking near infrared rays, two types of surface stabilizers, that is, polymer stabilizers and surfactants, are appropriately combined to form the properties of the composite particles (particle size Etc.) need to be adjusted. At this time, when only a surfactant (e.g., monodisperse surfactant, specifically sodium dodecyl sulfate) is used to prepare particles of uniform size, it is not possible to prepare composite particles of uniform size. However, it is difficult to achieve a near-infrared blocking effect because it has a nanoscale size (about 80 to 450 nm). Furthermore, even if the inorganic particles are initially mixed with the monomer solution and dispersed in the emulsion, it is not possible to prevent the separation of the inorganic particles during the reaction process, and in particular, a problem of causing the aggregation of the composite particles may be caused.

In addition, if only polymer stabilizers (PVP, PVA, etc.) are used, it is possible to suppress the separation of inorganic particles during the manufacturing process of the composite particles, but in this case, too large composite particles (even composite particles having a size of 10 μm or more) It may be difficult to manufacture and achieve a size effective for blocking near infrared rays. In addition, even when a polymer stabilizer is used, the problem that the inorganic particles are separated from the polymer polymerization process due to the difference in density between the inorganic particles and the monomers and precipitation phenomenon occurs may not be solved completely.

Therefore, in this embodiment, by using a combination of a polymer stabilizer and a low molecular surfactant so that the above-described problem is solved and the polymer-inorganic composite particles have a size suitable for blocking near infrared rays, a uniform size distribution while having a size of a micron level suitable for blocking near infrared rays Composite particles having characteristics are prepared, and the separation of inorganic particles and agglomeration of the generated composite particles can be suppressed as much as possible during the polymerization process.

In a specific embodiment, the inorganic particles in the polymerization process by introducing a certain amount of linear polymer that can be mixed with the monomers so that the inorganic particles are more evenly dispersed in the emulsion droplets composed of monomer-inorganic particles during the synthesis of the composite particles. (Specifically, nano-sized inorganic particles) can be induced to be dispersed in a stable state.

Formation of dispersion of inorganic particles

According to one embodiment, inorganic particles are dispersed in a mixture (mixed solution) containing a monomer compound and a crosslinking agent to form a dispersion. At this time, the crosslinking agent may affect the properties of the polymer matrix, and is synthesized into a branched polymer, a cross-linked polymer, or the like by controlling the concentration thereof. When a crosslinked polymer is produced, this is called gelation, and a linear polymer may be mixed to prevent the inorganic particles mixed with the initial monomer from leaving the emulsion. However, these linear polymers can prevent aggregation and separation of inorganic particles for a certain period of time during the initial reaction of the monomers, but aggregation and/or separation due to various reasons such as size, interfacial stability, and density difference of inorganic particles over time. This can happen. Therefore, when the monomer is prepared in the form of a linear polymer, it may be difficult to continuously suppress aggregation and/or separation. However, if the amount of the crosslinking agent is sufficient during the polymerization reaction of the monomer, the polymer is branched and gelled as the reaction proceeds, and the viscosity of the polymer matrix rises rapidly and the inorganic particles are dispersed in the polymer mattress. Can bring. Furthermore, the crosslinked polymer matrix may have an effect of maintaining the stability of particles in a cosmetic composition composed of various oil components.

According to an exemplary embodiment, as a monomer compound for preparing a polymer matrix, methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacryl Rate, pentyl acrylate, pentyl methacrylate, glycidyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, acrylic acid, methacrylic acid, and may be at least one selected from the group consisting of styrene.

In addition, the crosslinking agent (or crosslinking monomer) that can be used is a polyfunctional compound, such as ethylene glycol dimethacrylate, 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, and 1,3- Butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol di Acrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate, alkyl acrylate, 1,2-ethanediol dimethacrylate, 1,3- Propanediol methacrylate, 1,3-butanediol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol di At least one selected from the group consisting of methacrylate, polybutylene glycol dimethacrylate, allyl methacrylate, urethane acrylate, and diallyl maleate may be used.

At this time, the weight ratio of the monomer compound: the crosslinking agent in the mixture (mixed solution) may range from, for example, about 99.5 to 50: 0.5 to 50, and specifically about 99 to 80: about 1 to 20.

According to an exemplary embodiment, a linear polymer may be further added to a mixed solution of a monomer compound and a crosslinking agent for the purpose of improving the dispersion-maintenance property of inorganic particles added later. The molecular weight (M _w ) of such a linear polymer may be, for example, about 5,000 to 350,000, specifically about 20,000 to 200,000, and more specifically about 50,000 to 150,000.

In addition, according to exemplary embodiments, the linear polymer is, for example, polymethyl methacrylate, polymethyl acrylate, polystyrene, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polyethyl methacrylate. , Polybutyl acrylate, polybutyl methacrylate, polypentyl acrylate, polypentyl methacrylate, polyglycidyl methacrylate, polycyclohexyl acrylate, poly(2-ethylhexyl acrylate), polyacrylic acid , Polymethacrylic acid, and a combination thereof. However, the linear polymer may be advantageous in terms of miscibility to correspond to a polymer matrix formed by polymerization of a monomer or to use the same material, but it is not necessarily limited thereto, and any linear polymer that can be dissolved and uniformly mixed in a monomer compound You can also use

In this regard, the content (or addition amount) of the linear polymer may vary within the above-described range according to the content and size of the inorganic particles used. For example, in the case of near-infrared blocking Au-Al(OH) ₃ -TiO ₂ particles, they are non-spherical particles having a particle size of about 0.3 μm or more, and because the particle density is also large, about 5 to 20% by weight (specifically, about 10 to 15% by weight), which may correspond to the content of inorganic particles in the composite particles of about 1 to 10% by weight (specifically, 3 to 7% by weight). Therefore, when using a small amount of inorganic particles than the above-described amount, it is possible to reduce the amount of linear polymer used.

On the other hand, in the case of using metal oxide inorganic particles or pure gold (Au) nanoparticles with UV blocking function as inorganic particles, the precipitation rate is not fast, whereas these UV blocking metal oxide nanoparticles exhibit a hydrophobic tendency, so during polymerization reaction. Since the release rate from the emulsion is slow, the amount of polymer used can be minimized.

As described above, the amount of linear polymer used may be selected to improve dispersibility in the monomer mixture according to the type and properties of the inorganic particles. In this regard, when the amount of linear polymer is less than a certain level, inorganic particles cannot maintain the desired degree of dispersion stability in the monomer, whereas when used in an excessive amount, it takes a long time for the linear polymer to dissolve in the monomer. In addition to being uneconomical, the dispersion properties are no longer improved. Accordingly, the amount of the linear polymer added may be selected within the range of, for example, about 0.1 to 20% by weight, specifically about 1 to 15% by weight, and more specifically about 3 to 12% by weight, based on the monomer compound.

Meanwhile, a dispersion (dispersion) may be formed by adding inorganic particles to the monomer mixture prepared through the above procedure. As described above, there is a difference in the near-infrared ray or ultraviolet ray blocking effect depending on the content of inorganic particles, but when the content exceeds a certain amount, the inorganic particles are not uniformly dispersed in the composite particles. May decrease. In consideration of this, the content of the inorganic particles in the inorganic particle-containing dispersion is, for example, about 0.05 to 10% by weight, specifically about 0.5 to 8% by weight, more specifically in the range of 1 to 5% by weight based on the total weight of the dispersion. Can be properly adjusted within.

In an exemplary embodiment, the inorganic particles are preferably uniformly dispersed in the monomer mixture, and in the exemplary embodiment, known in the art such as ultrasonic irradiation (sonificationm), homogenizer, high speed mixer (mechanical mixer), etc. You can use means. For example, ultrasonic irradiation induces high-frequency mechanical waves (ultrasonic waves) into a predetermined space or device to vibrate, and as a result, inorganic particles in a mixture containing a monomer compound can be uniformly dispersed.

According to one embodiment, an initiator is added to the inorganic particle-containing dispersion (dispersion) formed as described above. Such initiators are known in the art, such as 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylisobutyronitrile), 2,2-azobis ( 2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide It may be at least one selected from the group consisting of oxide, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisobutyrate.

At this time, the initiator may be used in an appropriate amount based on the monomer compound, for example, in the range of about 0.1 to 5 mol%, specifically about 0.5 to 3 mol%, and more specifically about 1 to 2 mol%. However, the above range may be understood in an exemplary sense.

Preparation of aqueous solution containing a combination of a polymer stabilizer and a surfactant

According to one embodiment, an aqueous solution containing a combination of a polymeric stabilizer and a surfactant is prepared for the purpose of forming an emulsion by contacting with the dispersion to which an initiator is added, and controlling to have a desired particle size. If neither the polymer stabilizer nor the surfactant is used, the oil phase and the aqueous phase are separated, making it difficult to perform an emulsification or emulsion polymerization reaction. At this time, the aqueous medium may be water, and may include, for example, pure water, tap water, well water, spring water, fresh water, and water treated in various ways. Examples of such water treatment may include purification, heating, sterilization, filtration, and ion exchange.

According to an exemplary embodiment, the aqueous solution containing a combination of a polymeric stabilizer and a surfactant is selected within the range of, for example, about 50 to 100°C, specifically about 65 to 90°C, and more specifically about 70 to 85°C. Since it can be maintained at a temperature, it is possible to maximally dissolve the two types of interfacial stabilizer components in the aqueous medium.

According to an exemplary embodiment, the polymer stabilizer is easily adsorbed on the surface of the monomer droplet during the emulsion polymerization process, thereby providing a stereoscopic stabilizing effect, thereby stabilizing the emulsion. That is, through the addition of a polymer stabilizer, the viscosity of the solution increases, and a mechanism to stabilize and protect the oil component can be achieved.

In this regard, the polymeric stabilizer may be, for example, one having a molecular weight (M _w ) of at least about 10,000, specifically, about 20,000 to 2,000,000, more specifically about 50,000 to 200,000), and if the molecular weight is too small, the emulsion It may be difficult to effectively stabilize for a long time, and if the molecular weight is too large, it may be desirable to have a molecular weight in the above-described range because a problem in that the size of the particles cannot be effectively controlled due to an increase in viscosity may be caused. However, in the case of a polymer stabilizer having too much water solubility, it may be advantageous to select an appropriate type since it is difficult to cause adsorption because the interfacial attraction is small at the interface of the monomer droplet. According to an exemplary embodiment, the polymer stabilizer is polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyvinyl acetate (PVAc), polyacrylic acid (PAA), and It may be at least one selected from the group consisting of polyethylene oxide (PEO). These polymers primarily prevent fusion and agglomeration of emulsion droplets formed by increasing the viscosity of the emulsion solution, and in the case of polymers having a chemical component having low interfacial energy with the oil phase, a loop-tail-train (or It is adsorbed in the form of pancake) to stably stabilize the monomer emulsion.

On the other hand, a surfactant is a material that stabilizes the interface by having a hydrophilic head group and a hydrophobic tail group at the same time, and stabilizes the interface between the oil phase and the aqueous phase due to the amphiphilic component. Depending on the ionic surfactant (cationic (cationic) surfactant, anionic (anionic) surfactant and amphoteric (amphoteric) surfactant), and can be classified into a non-ionic (non-ionic) surfactant. In this embodiment, at least one of these surfactants may be selected and used, wherein the surfactant is, for example, about 1500 or less (specifically, about 100 to 1400, more specifically about 200 to 1000) of molecular weight (M _w ). If the molecular weight of the surfactant is too large, it may be an obstacle to implementing the advantage of controlling the droplet size to a desired level in combination with the above-described polymer stabilizer.

In addition, the surfactant may be a type having an HLB of about 5 to 40, specifically about 10 to 35, more specifically about 15 to 30), and any combination within the HLB range is possible. At this time, when the HLB range is too low or high, it may be advantageous to have the above-described range, as interfacial stability is unstable, and it may cause a problem that is difficult to stabilize while maintaining the emulsion droplet at a constant size.

Illustratively, the surfactant is, for example, sodium dodecyl sulfate (SDS), sodium lauryl ether sulfate (SLES), ammonium lauryl sulfate (ALS), and cetyl. Trimethylammonium bromide (cetyltrimethylammonium bromide; CTAB), dodecyl trimethylammonium bromide (dodecyltrimethylammonium bromide; DTAB), myristyl trimethylammonium bromide (myristyl trimethylammonium bromide; TTAB) and at least one selected from the group consisting of polysorbate. In particular, anionic surfactants in which the hydrophilic portion becomes anions by ionization in water, and vice versa, cationic surfactants and ionic surfactants, may be ionized in an aqueous solution to provide an electrostatic stabilizing effect. Alternatively, nonionic surfactants such as polysorbate (specifically, polysorbate 20, 40, 60, 80, etc.) are commercially available under a trade name such as TWEEN 20 in the art, and are effective in stabilizing emulsions.

According to an exemplary embodiment, the weight ratio of the polymer stabilizer: surfactant in the aqueous solution containing the combination of the polymer stabilizer and surfactant is, for example, 1: about 0.1 to 1.25, specifically 1: about 0.2 to 1, more Specifically, 1: may be in the range of about 0.5 to 0.75. In this regard, when the ratio of the polymer stabilizer to the surfactant is less than a certain level or exceeds a certain level, it may be difficult to achieve an effective particle diameter distribution for blocking the near-infrared rays of the emulsion particles.In addition, depending on the type of the polymer stabilizer and the surfactant, The level of blending ratio desired between the two ingredients can vary. For example, even if the same polymer stabilizer (e.g., PVA) is used, the case of using SDS as a surfactant and the case of using polysorbate are distinguished within the above-described range in order to achieve effective particle size for blocking near infrared rays. May be required. Therefore, it is advantageous to control or select the blending ratio between the two components within the range given above so that the composite particles or polymer matrix particles have an effective size for blocking near infrared rays. More specifically, it may be desirable to select a blending ratio between the two components that enables the synthesis of composite particles or polymer matrix in the size range of about 1 to 3 μm.

In addition, the concentration of the polymeric stabilizer in the aqueous solution may range from, for example, about 1 to 5% by weight, specifically about 1.8 to 3% by weight, and more specifically about 2 to 2.5% by weight. In addition, the concentration of the surfactant in the aqueous solution may be in the range of, for example, about 0.5 to 2.5% by weight, specifically about 0.7 to 2% by weight, and more specifically 1 to 1.5% by weight.

In this way, in preparing an aqueous solution by adding each of a polymer stabilizer and a surfactant to an aqueous medium (or water), a stirring means known in the art to reach a state (equilibrium state) in which the surface stabilizer can be uniformly dissolved or distributed, For example, ultrasonic irradiation (sonificationm), homogenizer, high speed mixer (mechanical mixer), etc. can be applied.

polymerization

In one embodiment, the initiator-added dispersion prepared above is contacted with an aqueous solution containing a combination of a polymer stabilizer and a surfactant to form an emulsion, and a polymerization reaction is performed. Since the basic principle of the emulsion polymerization or emulsion polymerization reaction is known in the art, details of the technical principle will be omitted.

According to an exemplary embodiment, the weight ratio of the dispersion to which an initiator is added: an aqueous solution containing a combination of a polymer stabilizer and a surfactant is, for example, 1: about 3 to 100, specifically 1: about 3 to 50, more Specifically, 1: may be within the range of about 5 to 20, it can be adjusted in consideration of the concentration of each of the polymer stabilizer and surfactant in the aqueous solution.

Meanwhile, the polymerization temperature during emulsion polymerization may be, for example, about 70 to 100°C, specifically about 75 to 95°C, and more specifically about 80 to 90°C. As the polymerization reaction proceeds, the size of the polymer particles increases, so it may be desirable to adjust the polymerization time range. In this regard, an exemplary polymerization reaction time may be in the range of about 0.3 to 6 hours, specifically about 0.5 to 5 hours, and more specifically about 1 to 4 hours, but the present invention is not necessarily limited thereto.

According to an exemplary embodiment, in addition to the combination of the two types of additives (polymer stabilizer and surfactant) described above to control the size of the composite particles, external energy (specifically, mechanical energy) is selectively introduced to provide better dispersion. It can provide an effect. To this end, a dispersing means known in the art such as a homogenizer, a high pressure homogenizer, an ultrasonic disperser, and a high-speed mixer may be used.

According to a specific embodiment, by maintaining the rotational speed of the homogenizer at a high speed (by applying high energy mechanical energy) to homogenize the emulsion, the composite particles can be optimized to have a size effective for blocking near infrared rays. At this time, the rotation speed of the homogenizer may be, for example, about 1,000 to 20,000 rpm, specifically about 3,000 to 15,000 rpm, and more specifically about 5,000 to 12,000 rpm.

Separation, cleaning and/or drying steps (optional)

The composite particles prepared according to the above-described procedure go through a separation process known in the art, for example, a solid-liquid separation process. Examples of such separation processes include filtration, reduced pressure filtration, decantation, pressure filtration, and centrifugation. Separation, spray drying, and the like.

In addition, impurities contained in the composite particles can be removed at least once by using a solvent or the like for the separated solid content. At this time, the organic solvent used in the precipitation process may be used as the solvent. In this way, when the solid content washing process is finished, a drying step may be performed to remove the residual solvent contained in the secondary particles. Such drying steps include, for example, air drying, thermal drying, vacuum drying, freeze drying. And the like, a drying method known in the art may be used. In this regard, the drying step may be performed at a temperature in the range of, for example, 20 to 100°C, specifically room temperature to about 80°C.

According to one embodiment of the present disclosure, it is not necessary to perform all of the above-described separation, washing and drying processes, and at least one may be omitted in some cases.

C. Cosmetics manufacturing

According to one embodiment, the polymer-inorganic composite particles described above may be added or mixed in a cosmetic to provide near-infrared blocking and/or near-infrared-ultraviolet blocking effects. For example, the composite particles may be contained in a range of about 0.01 to 10% by weight, specifically about 0.1 to 5% by weight, and more specifically about 0.5 to 2% by weight, based on the total weight of the cosmetic.

Such cosmetic compositions can be prepared in any formulation known in the art, for example, solutions, suspensions, emulsions, pastes, gels, creams, lotions, powders, soaps, surfactant-containing cleansing, oils, powder foundations. , Emulsion foundation, wax foundation, or may be in the form of a spray formulation. Specifically, lotion, cream, essence, cleansing foam, cleansing water, pack, body lotion, body oil, body gel, shampoo, conditioner, hair conditioner, hair gel, foundation, lipstick, mascara, pack mask, makeup base, etc. can do. In addition, it may further contain additive components known in the art, such as stabilizers, solubilizers, conventional adjuvants such as vitamins, pigments and flavors, carriers, and the like.

For example, in the case of a solution or emulsion, a solvent, a solubilizing agent or an emulsifying agent may be used as a carrier component. Specifically, water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene Glycol, 1,3-butylglycol oil, glycerol aliphatic ester, polyethylene glycol and/or fatty acid ester of sorbitan can be used.

In addition, binders including starch, tragacanth rubber, gelatin, molasses, polyvinyl alcohol, polyvinyl ether, polyvinyl pyrrolidone, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose and carboxymethyl cellulose; Agar, starch, gelatin powder, carboxymethyl cellulose sodium, carboxymethyl cellulose calcium, crystalline cellulose, calcium carbonate, sodium hydrogen carbonate and sodium alginate; Lubricants including magnesium stearate, talc and hydrogenated vegetable oil; And a colorant. In addition, lactose, glucose, sucrose, mannitol, potato starch, corn starch, calcium carbonate, calcium phosphate, and cellulose may be used as the carrier. In addition, additives such as a stabilizer, a dissolution aid, an auxiliary agent such as a transdermal absorption accelerator, and an additive such as a preservative may be further contained.

The present invention may be more clearly understood by the following examples, and the following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Example 1

Preparation of polymer particles

-Preparation of polymethyl methacrylate (PMMA) polymer particles

80 aqueous solutions containing 2% by weight of polyvinyl alcohol (dispersion stabilizer; Sigma Aldrich, M _w :85,000-124,000) and 1% by weight of sodium dodecyl sulfate (surfactant; Wako pure chemical industries) based on the total aqueous solution. It was allowed to equilibrate under stirring conditions at °C (aqueous stabilizer solution).

Separately, methyl methacrylate (monomer), polymethyl methacrylate (linear polymer; Sigma Aldrich, M _w : ~120,000) and ethylene glycol dimethacrylate ( A crosslinking agent; Sigma Aldrich) was mixed and added, and then the reactants were evenly dissolved to prepare a monomer mixture. Thereafter, 1 mol% of azobisisobutyronitrile (initiator; Junsei) was added to the monomer mixture and dispersed. Then, 11.6 g of the monomer mixture to which the initiator was added was added to 100 g of the previously prepared stabilizer aqueous solution to proceed with the emulsification process, and reacted for 4 hours or more to prepare polymer particles.

Examples 2 to 4

Synthesis of polymer-inorganic composite particles

As an inorganic particle for blocking near infrared rays, (i) TiO ₂ (Al(OH) ₃ -TiO ₂ ) containing aluminum hydroxide (Ishihara Sangyo Kaisha); (ii) TiO ₂ containing aluminum hydroxide and coated with gold nanoparticles on the surface (Au-Al(OH) ₃ -TiO ₂ ); And (iii) Au nanoparticles were used.

In this regard, the Au-Al(OH) ₃ -TiO ₂ particles are coated with HAuCl ₄ through a reduction reaction using ascorbic acid (Sigma Aldrich) on the Al(OH) ₃ -TiO ₂ particle surface. Was prepared.

In addition, in the case of Au nanoparticles, HAuCl ₄ (gold precursor; Sigma Aldrich) and trisodium citrate (trisodium citrate, reducing agent; Fisher scientific) were dissolved in an aqueous solution, mixed, and then obtained by reducing reaction at high temperature. At this time, the size of the Au nanoparticles was about 40 nm.

TiO ₂ (M160, SACHTLEBEN) particles were used as the inorganic particles for blocking ultraviolet rays.

Example 2

Preparation of polymer-inorganic composite particles containing Au-Al(OH) ₃ -TiO ₂ inorganic particles

Based on the total aqueous solution, 2% by weight of polyvinyl alcohol (dispersion stabilizer) and 1% by weight of sodium dodecyl sulfate (surfactant) were added to water and equilibrated under stirring conditions at 80°C (aqueous stabilizer).

Separately, methyl methacrylate (monomer), polymethyl methacrylate (linear polymer; M _w : ~120,000) and ethylene glycol dimethacrylate (crosslinking agent) of 10% by weight relative to the monomer, and 5% by weight of inorganic particles After (Au-Al(OH) ₃ -TiO ₂ ) is added, the temperature is raised to 50°C while irradiating with ultrasonic waves using a sonicator to uniformly distribute the reactants, thereby distributing the monomer mixture containing inorganic particles (dispersion liquid). ) Was prepared. Thereafter, 1 mol% of azobisisobutyronitrile (initiator) was added and dispersed to the monomer mixture (dispersion).

Then, 12.1 g of the monomer mixture (dispersion) to which the initiator was added was added to 100 g of the previously prepared stabilizer aqueous solution to proceed with the emulsification process, and then reacted for at least 4 hours to prepare polymer-inorganic composite particles.

Example 3

Preparation of polymer-inorganic composite particles with gold (Au) nanoparticles introduced

Based on the total aqueous solution, 2% by weight of polyvinyl alcohol (dispersion stabilizer) and 1% by weight of sodium dodecyl sulfate (surfactant) were added to water and equilibrated under stirring conditions at 80°C (aqueous stabilizer).

Separately, after adding methyl methacrylate (monomer), 10 wt% of polymethyl methacrylate (linear polymer) and ethylene glycol dimethacrylate (crosslinking agent), and 0.05 wt% of gold nanoparticles relative to the monomer, The temperature was raised to 50° C. while irradiating ultrasonic waves using a sonicator to uniformly distribute the reactants to prepare a monomer mixture (dispersion) containing inorganic particles. Thereafter, 1 mol% of azobisisobutyronitrile (initiator) was added and dispersed to the monomer mixture (dispersion).

Then, 11.6 g of the monomer mixture (dispersion) to which the initiator was added was added to 100 g of the previously prepared stabilizer aqueous solution to proceed with the emulsification process and then reacted for 4 hours or more to prepare polymer-inorganic composite particles.

Example 4

Preparation of polymer-inorganic composite particles into which Al(OH) ₃ -TiO ₂ inorganic particles are introduced

Polymer-inorganic composite particles were prepared in the same manner as in Example 2, except that Al(OH) ₃ -TiO ₂ was used instead of Au-Al(OH) ₃ -TiO ₂ as inorganic particles.

Example 5

Preparation of polymer-inorganic composite particles incorporating metal oxide inorganic particles for UV protection

Based on the total aqueous solution, 2% by weight of polyvinyl alcohol (dispersion stabilizer) and 1% by weight of sodium dodecyl sulfate (surfactant) were added to water and equilibrated under stirring conditions at 80°C (aqueous stabilizer).

Separately, methyl methacrylate (monomer), polymethyl methacrylate (linear polymer; M _w : ~120,000) and ethylene glycol dimethacrylate (crosslinking agent) of 10% by weight relative to the monomer, and 5% by weight of inorganic particles After (TiO ₂ ) was added, the temperature was raised to 50° C. while irradiating ultrasonic waves using a sonicator to uniformly distribute the reactants to prepare a monomer mixture (dispersion) containing inorganic particles. Thereafter, 1 mol% of azobisisobutyronitrile (initiator) was added and dispersed to the monomer mixture (dispersion).

Then, 12.1 g of the monomer mixture (dispersion) to which the initiator was added was added to 100 g of the previously prepared stabilizer aqueous solution to proceed with the emulsification process, and then reacted for at least 4 hours to prepare polymer-inorganic composite particles.

analysis

-Analysis of particle size and characteristics of polymer-inorganic composite particles

The synthesized polymer-inorganic composite particles were separated and purified by an aqueous solution, and then sufficiently redispersed in distilled water and observed using optical microscopy (OLYMPUS BX51). Photos were taken through dark field mode to determine whether inorganic particles were contained. The measured image is Image J(National Institutes of Health, USA) The average value was obtained by measuring the size of a number of composite particles.

Further, the composite particles were diluted to an appropriate concentration, dropped onto a silicon substrate, and dried in a drying oven. The completely dried silicon substrate was observed using a scanning electron microscopy (SEM) equipment.

On the other hand, in the case of the polymer-inorganic composite particles containing Au nanoparticles (Example 3), it was confirmed whether the gold nanoparticles were incorporated using a transmission electron microscopy (TEM).

-Evaluation of light blocking ability of polymer-inorganic composite particles

After sufficiently dispersing the recovered and purified polymer-inorganic composite particles in distilled water, it was diluted to an appropriate concentration, and ultraviolet-visible-near-infrared region (280-1350) using UV-vis-NIR spectroscopy (JASCO V-670) equipment. nm) was measured to evaluate the light blocking ability, and the result was derived by repeating the process.

In addition, the recovered and purified polymer-inorganic composite particles were dispersed in distilled water to prepare a 10% by weight aqueous solution, and then the cosmetic formulation and the polymer-inorganic composite particle aqueous solution were mixed at 60° C. in an 8:2 weight ratio. The cosmetic composition used is shown in Table 1 below.

Raw material name (INCI Name) Content (% by weight) Disodium EDTA 0.05 Propanediol 5 Tromethanmine 0.05 Carbomer 0.08 Hydroxyethyl acrylate
/sodium acryloyldimethyl taurate copolymer 0.3 Ethylhexylglycerin 0.05 1,2-hexandiol One Ethanol 4 Homosalate 3 Octocrylene 8 Butyl methoxydibenzoylmethane 2.5 C12-20 alkyl glucoside
/C14-22 alcohols One Glyceryl stearate citrate 0.5 Methyl trimethicone 2 Water to 100

As for the cosmetic formulation thus mixed, the same weight (0.025 g) was dropped on a slide glass and then covered with a cover glass to prepare a sample. Then, the UV-vis-NIR spectroscopy (JASCO V-670) equipment was used to measure the spectrum for the ultraviolet-visible-near-infrared region (280-1400 nm) to evaluate the light blocking ability, and the process was repeated. The result was derived.

Evaluation of light blocking ability of polymers and composite particles according to size

The light blocking characteristics when the size of the polymethyl methacrylate (PMMA) particles synthesized according to Example 1 is changed are shown in FIG. 2. At this time, the polymer particles exhibited monodispersity distribution as particles having constant particle size characteristics within the size range of the nano level to the micron level.

Referring to the drawing, it was confirmed that the blocking effect of the PMMA particles in the visible and near infrared regions increased as the particle size increased. Therefore, when the size (or diameter) of the polymer particles is adjusted within the range of approximately 1 to 3 μm, it can be confirmed that it is effective in blocking light in the near-infrared band.

Au-Al(OH) ₃ -TiO ₂ Evaluation of light blocking ability of PMMA-inorganic composite particles containing

According to Example 2, a polymer-inorganic composite in which aluminum hydroxide is contained in a PMMA matrix, and gold (Au) nanoparticles are coated on the surface of TiO ₂ (Au-Al(OH) ₃ -TiO ₂ ) inorganic nanoparticles are dispersed 3 shows optical micrographs of each of the particles and the PMMA polymer matrix particles (PMMA control) that do not contain inorganic particles prepared in Example 1 as a control under bright field and dark field.

At this time, the inorganic particles are prepared by coating gold (Au) on the surface of Al(OH) ₃ -TiO ₂ by a wet method in order to enhance the near-infrared blocking ability by the LSPR effect. The amount of the Au-Al(OH) ₃ -TiO ₂ inorganic particles used in the composite particles was 5% by weight. As a control, the PMMA particles prepared in Example 1 were used for evaluation.

Referring to the drawing, when contrasting the bright field and dark field optical micrographs, the PMMA particles and the polymer-inorganic composite particles have almost the same size, whereas inorganic particles not found in the PMMA particles are It can be seen that it is uniformly mixed (dispersed) inside the composite particles. Specifically, in the case of PMMA particles, the average particle diameter was 1.79±0.77 μm, and in the case of the composite particles containing Au-Al(OH) ₃ -TiO ₂ particles, the average particle diameter was measured to be 1.67±0.59 μm.

As a result of the measurement, it was confirmed that most of the particles exhibited a particle size of 1 to 3 µm, regardless of whether inorganic particles were contained, and in particular, all particles had a particle size within 3 µm.

According to Example 2, a polymer-inorganic composite particle in which Au-Al(OH) ₃ -TiO ₂ inorganic particles are dispersed in a PMMA matrix, and a control that does not contain Au-Al(OH) ₃ -TiO ₂ inorganic particles (PMMA Particles) are shown in FIG. 4 in comparison with each light blocking property. In addition, the results summarized by quantifying the degree of light blocking at a representative wavelength are shown in Table 2 below.

1000 nm 1200 nm PMMA (no inorganic particles) 0.309 0.263 Au-Al(OH) ₃ -TiO ₂ @PMMA composite particles (Au-Al(OH) ₃ -TiO ₂ 5% by weight) 0.327 0.307

According to the above figure, it can be seen that PMMA particles as a control exhibit near-infrared blocking ability. In addition, in the case of PMMA-inorganic composite particles in which Au-Al(OH) ₃ -TiO ₂ inorganic particles are contained in 5% by weight in the composite particles, the near-infrared blocking ability is 6% at a wavelength of 1000 nm compared to the control group. , And at a wavelength of 1200 nm, it increased by 17%. At this time, the concentration of the Au-Al(OH) ₃ -TiO ₂ particles is 3 µg/mL, which is the pure Au-Al(OH) ₃ -TiO ₂ concentration required to exhibit the same effect at a wavelength of 1000 nm. Compared with the concentration of 38 μg/mL, it can be seen that the content of inorganic particles used to achieve the same near-infrared blocking ability is significantly reduced.

Evaluation of light blocking ability of PMMA-inorganic composite particles containing Au nanoparticles

According to Example 3, the SEM and TEM images of the polymer-inorganic composite particles in which Au nanoparticles are dispersed in a PMMA matrix are shown in FIG. 5.

As shown in the figure, the composite particles prepared according to the examples have a smooth spherical shape, and in particular, TEM images show that gold (Au) nanoparticles are contained in the PMMA matrix. The average particle diameter of the PMMA-inorganic composite particles containing gold nanoparticles was 1.81ㅁ0.73 µm, and the amount of Au nanoparticles in the composite particles was 0.053% by weight. As a result of the evaluation, most of the composite particles exhibited a particle size of 1 to 3 µm, regardless of whether the inorganic particles were contained, and all particles had a particle size within 3 µm.

According to Example 3, a graph comparing the light blocking characteristics of each of the polymer-inorganic composite particles in which Au nanoparticles are dispersed in a PMMA matrix, and a control (PMMA particles) not containing Au nanoparticles is shown in FIG. 6. In addition, the results obtained by quantifying the degree of light blocking in a representative wavelength region are shown in Table 3 below.

280 nmm 360 nm 1000 nm 1200 nm PMMA(Control) 0.282 0.292 0.309 0.263 Au@PMMA composite particles 0.355 0.333 0.314 0.279

As a result of the measurement, in the near-infrared region of 1000 nm and 1200 nm, the light blocking ability was increased by 1.6% and 6%, respectively, compared to the control group. Despite the small amount of gold nanoparticles contained in the polymer matrix, it showed excellent near-infrared blocking ability. .

Moreover, in the case of pure gold nanoparticles, as well as the near-infrared blocking effect, unlike PMMA particles (control) containing no inorganic particles, 26% at 280 nm UV-B region) and 14 at 360 nm (UV-A region). It was confirmed that a synergistic effect of% light blocking ability can be obtained.

These results suggest that when an appropriate form of gold nanoparticles is introduced into the composite particle, the near-infrared blocking effect can be mainly strengthened, but not only this, it also provides a certain level or higher blocking effect even for light in the ultraviolet region, which is an inorganic particle. This suggests that unexpected synergistic effects can be achieved in combination with a polymer matrix of certain properties.

Al(OH) ₃ -TiO ₂ Evaluation of light blocking ability of PMMA-inorganic composite particles containing particles

According to Example 4, an optical microscope image of a polymer-inorganic composite particle in which TiO ₂ (Al(OH) ₃ -TiO ₂ ) inorganic nanoparticles containing aluminum hydroxide in a PMMA matrix is dispersed is shown in FIG. 7A. Referring to the drawing, the average particle diameter of the composite particles was 1.83ㅁ0.60 µm, and the amount of Al(OH) ₃ -TiO ₂ contained in the composite particles was 5% by weight. In particular, it was confirmed that most of the particles have a particle size of 1 to 3 µm, and all particles have a particle size within 3 µm, regardless of whether inorganic particles are contained.

In addition, in the PMMA matrix prepared according to Example 4 TiO ₂ containing aluminum hydroxide (Al(OH) ₃ -TiO ₂ ) The light blocking characteristics when the size of the polymer-inorganic composite particles in which inorganic particles are dispersed is changed in FIG. Indicated. According to the drawing, it can be seen that the light blocking effect for the near-infrared band (750-1350 nm) is relatively high when the composite polymer particle size is in the range of 1 to 3 μm (red dotted line and solid line). Particularly, even when the average particle diameter is 1.8 µm and the same (blue solid line and red solid line), the particle size distribution is wide, so when particles exceeding 3 µm are included (blue solid line), the near-infrared blocking effect is relatively lowered. I can. On the other hand, it is noteworthy that when the particle diameter of the composite polymer particles has a distribution close to 1 µm (green solid line), an additional UV blocking effect can be obtained.

Meanwhile, according to Example 4, a polymer-inorganic composite particle in which Al(OH) ₃ -TiO ₂ inorganic particles are dispersed in a PMMA matrix, and a control (PMMA particle) that does not contain Al(OH) ₃ -TiO ₂ inorganic particles A graph comparing the light blocking characteristics of is shown in FIG. 8. In addition, the results obtained by quantifying the degree of light blocking in a representative wavelength range are shown in Table 4 below.

1000 nm 1200 nm PMMA (not including inorganic particles) 0.309 0.263 Al(OH) ₃ -TiO ₂ @PMMA composite particles
(5% by weight of inorganic particles) 0.322 0.289

According to the figures and tables, when the inorganic particles are included, the light blocking ability is increased by 4% and 14% at the 1000 nm wavelength and 1200 nm wavelength, respectively, in the near-infrared ray blocking region, compared to the case where the inorganic particles are not included. At this time, the concentration of Al(OH) ₃ -TiO ₂ particles is 3 μg/mL, which is equivalent to 44 μg/mL, which is the concentration of pure Al(OH) ₃ -TiO ₂ required to exhibit the same effect at 1000 nm wavelength. It was confirmed that the content of inorganic particles required to achieve near-infrared blocking ability was significantly reduced.

TiO for UV protection ₂ Evaluation of light blocking ability of PMMA-inorganic composite particles containing particles

According to Example 5, an optical microscope image of a polymer-inorganic composite particle in which TiO ₂ inorganic particles for UV blocking are dispersed in a PMMA matrix is shown in FIG. 9.

Referring to the drawing, the average particle diameter of the composite particles was 1.64 ㅁ 0.64 µm, and the amount of TiO ₂ contained in the composite particles was 5% by weight. Regardless of whether inorganic particles are contained, most of the particles have a particle diameter of 1 to 3 µm, and all particles have a particle size within 3 µm.

On the other hand, according to Example 5, a graph comparing the light-blocking characteristics of the polymer-inorganic composite particles in which TiO ₂ inorganic particles for blocking UV rays are dispersed in a PMMA matrix, and a control (PMMA particles) not containing TiO ₂ inorganic particles It is shown in Figure 10. In addition, the results obtained by quantifying the degree of light blocking in a representative wavelength region are shown in Table 5 below.

280 nmm 360 nm 1000 nm 1200 nm PMMA(Control) 0.282 0.292 0.309 0.263 TiO ₂ @PMMA composite particles
(5% by weight of inorganic particles) 0.316 0.377 0.300 0.247

According to the above drawings and tables, when inorganic particles (inorganic nanoparticles) are contained, the light blocking ability is somewhat (3% and 6) in the near-infrared region of 1000 nm wavelength and 1200 nm wavelength compared to the case of not containing them (control group). %) decreased, but the blocking ability increased by 12% and 29%, respectively, in the ultraviolet region of 280 nm wavelength (UV-B region) and 360 nm wavelength (UV-A region). At this time, the concentration of TiO ₂ particles is 3 µg/mL, and the content of inorganic particles can be significantly reduced compared to 76 µg/mL, which is the concentration of pure TiO ₂ required to exhibit the same effect at a wavelength of 1000 nm. Furthermore, it was confirmed that the composite particles could block near-infrared rays and ultraviolet rays at the same time by containing the inorganic particles for blocking ultraviolet rays.

Al(OH) depending on the concentration of surfactant ₃ -TiO ₂ @PMMA Evaluation of properties of composite particles

-When PVA is used as a polymer stabilizer and Tween 20, a polysorbate-based surfactant, is used as the surfactant, the composite particles (Al(OH) by changing the concentration of Tween 20 at a fixed PVA concentration (2% by weight)) ) ₃ -TiO ₂ @PMMA) is shown in Figure 11a and Table 6 below. In addition, the light blocking characteristics (UV-VIS-NIR Spectrum) were evaluated and shown in FIG. 11B.

PVA concentration: 2% by weight Tween 20 concentration (% by weight) 0 0.5 0.6 0.75 One Average particle diameter (μm) 9.8 1.8 1.7 1.1 1.0 Particle diameter range (μm) 6.2-13.4 1.0-3.4 1.4-2.1 1.0-1.7 0.9-1.1

According to the drawings and tables, when using Tween 20, a nonionic polysorbate surfactant, as a surfactant, the size of the composite particle is significant as its concentration gradually increases within the range of 0 to 1% by weight. Will be affected. In particular, it is judged to have a particle size (specifically 1 to 3 μm) particularly suitable for blocking near infrared rays at 0.6% by weight and 0.75% by weight.

However, when PVA is used alone (when Tween 20 is not used), sufficient surface activity cannot be obtained, and thus composite particles having a size suitable for blocking near infrared rays cannot be obtained. On the other hand, if the concentration of Tween 20 is too large, the size of the composite particles can be reduced and the dispersion stability of the particles can be slightly improved. It was confirmed that it could not be achieved.

Referring to FIG. 11B, when the concentration of Tween 20 is 0.6% by weight (yellow line), the particle size distribution can maximize the near-infrared blocking effect, which has a polymer matrix particle adjusted to an appropriate size and a near-infrared blocking effect. This corresponds to the result of combining inorganic particles.

-When PVA is used as a polymer stabilizer and SDS is used as an anionic surfactant, composite particles (Al(OH) ₃ -TiO ₂ @PMMA) by changing the concentration of SDS at a fixed PVA concentration (2% by weight) ) Is shown in Figure 12a and Figure 12b, respectively. In addition, the size of the composite particles according to the SDS concentration was measured and shown in Table 7 below.

PVA concentration: 2% by weight SDS concentration (% by weight) 0 0.1 0.5 0.75 One 3 Average particle diameter (μm) 9.8 2.5 2.2 2.1 1.8 Composite particles
Agglomeration Particle diameter range (μm) 6.2-13.4 0.6-4.5 1.1-3.3 1.2-3.0 1.2-2.4

According to the above table, when an appropriate amount of SDS as a surfactant is used together with PVA as a polymer stabilizer, composite particles having a size suitable for blocking near infrared rays can be synthesized.

Referring to FIG. 12A, when the SDS is used in an amount of 0.75% by weight and 1% by weight, respectively, as previously examined, composite particles having a size effective for blocking near infrared rays can be prepared. In particular, in the case of using 1% by weight of SDS, it can be confirmed that high-quality composite particles having a uniform particle size distribution were synthesized with a particle size distribution range of 1.2 to 2.4 µm and an average particle diameter of 1.8 µm, which is effective for blocking near infrared rays. have.

Meanwhile, referring to FIG. 12B, when SDS is not used or contained in an appropriate amount (0.1% by weight), the particle size range of the composite particles remarkably falls short or exceeds the appropriate range (specifically, 1 to 3 μm). In addition, when the SDS concentration was too high (3% by weight), a phenomenon in which the composite particles were aggregated was observed.

Al(OH) according to the concentration change of polymer stabilizer ₃ -TiO ₂ @PMMA Evaluation of properties of composite particles

When PVA is used as a polymer stabilizer and SDS is used as an anionic surfactant, composite particles according to changing the concentration of PVA at a fixed SDS concentration (1% by weight) (Al(OH) ₃ -TiO ₂ @PMMA) The size change of is shown in FIGS. 13A and 13B, respectively. In addition, the size of the composite particles according to the PVA concentration was measured and shown in Table 8 below.

SDS concentration: 1% by weight PVA concentration (% by weight) 0 One 2 5 Average particle diameter (μm) Agglomeration of composite particles Agglomeration of composite particles 1.8 0.8 Particle diameter range (μm) 1.2-2.4 0.81-0.87

13A and 13B, and according to the above table, when using a polymer stabilizer (PVA) of an appropriate concentration (i.e., 2% by weight) for a fixed SDS concentration, it was found that the particle size characteristics of the composite particles suitable for blocking near infrared rays were obtained. I can. However, when the PVA concentration was less than a certain level, agglomeration of the composite particles occurred. On the other hand, at too high a concentration of PVA, too small composite particles were formed, making it difficult to achieve a size suitable for the near-infrared blocking effect.

Al(OH) according to the change in the amount of linear polymer added ₃ -TiO ₂ @PMMA Evaluation of properties of composite particles

-When preparing polymer-inorganic composite particles in which Al(OH) ₃ -TiO ₂ is dispersed in PMMA matrix, the amount of linear polymer added to the monomer mixture (Al(OH) ₃ -TiO ₂ ): 5% by weight compared to the total of monomers and linear polymers ) Was evaluated for its effect on the dispersion stability. The results are shown in Figs. 14A and 14B.

According to FIG. 14A, when the linear polymer is added in an appropriate range, inorganic particles in the monomer mixture are stably dispersed. In addition, referring to FIG. 14B, when the concentration of the linear polymer is too low (not added or 0.05% by weight), the dispersion stability of the inorganic particles decreases due to the low viscosity of the monomer mixture, resulting in agglomeration of the inorganic particle-containing monomer mixture. Occurs. On the other hand, when the concentration of the linear polymer exceeds an appropriate level (30% by weight), the time required to dissolve in the monomer compound tends to increase by 5 times or more compared to when the linear polymer is added in an appropriate amount.

-The effect of the linear polymer addition on the synthesis process and properties of the polymer-inorganic composite particles in which Al(OH) ₃ -TiO ₂ was dispersed in the PMMA matrix was evaluated.

As a result of the analysis, if the linear polymer was not added, an emulsion could be formed during the emulsification process, although partial agglomeration of the monomer mixture occurred. However, when an excessive amount of linear polymer was added (30% by weight), a uniform emulsion was not formed during the emulsification process, and as a result, agglomeration of the composite particles occurred.

In addition, the results of evaluating the effect of the change in the addition amount of the linear polymer on the properties of the composite particles are shown in FIGS. 15A and 15B.

According to FIG. 15A, it was possible to prepare composite particles having a size optimized for near-infrared blocking by adding an appropriate amount of the linear polymer. On the other hand, referring to FIG. 15B, when the amount of linear polymer added is low, the tendency of the inorganic particles to detach is frequent, and when the amount of linear polymer added is too high, the tendency of aggregation of the composite particles due to the high viscosity of the monomer mixture was observed.

Based on the above results, the effect of the addition amount of the linear polymer on the production of composite particles is summarized in Table 9 below.

Linear polymer concentration (% by weight) 0 0.05 5 10 20 30 Experiment result
Decreased dispersion stability and aggregation of inorganic particles in monomer mixture Synthesis of composite particles without aggregation or separation of inorganic particles Increased dissolution time of linear polymer and aggregated composite particles

Au-Al(OH) ₃ -TiO ₂ Observation of light blocking performance in the formulation of polymer-inorganic composite particles containing inorganic particles

Cosmetics containing polymer-inorganic composite particles in which Au-Al(OH) ₃ -TiO ₂ inorganic particles are dispersed in the PMMA matrix, cosmetics containing PMMA particles that do not contain inorganic particles, and cosmetic formulations that do not contain particles The results of comparing each light blocking characteristic (100-Transmittance (%): a value obtained by subtracting the amount of transmitted light from the total amount of incident light) are shown in FIG. 16, and these results are numerically summarized in Table 10 below.

1000 nm 1200 nm Cosmetic formulation 19.0% 19.0% Cosmetic formulation containing PMMA particles
(Contains 2% by weight of PMMA particles) 24.2% 23.5% Cosmetic formulation containing Au-Al(OH) ₃ -TiO ₂ @PMMA particles (contains 2% by weight of composite particles) 28.8%
(1.52 times increase) 27.5%
(1.45 times increase)

Referring to the drawing, when pure PMMA particles were contained in a cosmetic formulation, about 24.2% and about 23.5% blocking effects were exhibited at a wavelength of 1000 nm and 1200 nm, respectively, based on an absolute value. In addition, when the composite particles were contained in the cosmetic formulation, a blocking effect of 28.8% and 27.5% was obtained, respectively. On the other hand, in the case of the cosmetic formulation that did not contain both polymer particles and composite particles, the light blocking effect of 19% was exhibited at 1000 nm wavelength and 1200 nm wavelength, respectively. As described above, it can be seen that the cosmetic formulation containing the composite particles according to the present embodiment improves the blocking effect by 1.52 times and 1.45 times at 1000 nm wavelength and 1200 nm wavelength, respectively, compared to the case where the particles are not included.

In conclusion, it was confirmed that the polymer-inorganic composite particles according to the present example not only exhibited good dispersion properties in aqueous media, but also effectively blocked near infrared rays in emulsion formulations containing cosmetics.

Simple modifications or changes of the present invention can be easily used by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (20)

A spherical polymer matrix having a size in the range of 1 to 3 µm to enable near-infrared blocking; And
Inorganic particles dispersed in the polymer matrix;
As a polymer-inorganic composite particle comprising a,
(i) In order to increase the near-infrared blocking effect of the polymer-inorganic composite particles, the inorganic particles have a size of 20 to 1000 nm and contain at least one metal element selected from the group consisting of Au, Al and Ag, or , or
(ii) In order to provide an effect of simultaneously blocking near-infrared rays and ultraviolet rays to the polymer-inorganic composite particles, the inorganic particles have a size of 20 to 100 nm, and TiO ₂ , ZnO, ZnO ₂ , CuO, CuO ₂ , Al At least one is selected from the group consisting of ₂ O ₃ , Al(OH) ₃ , CeO ₂ , Ce ₂ O ₃ , Fe ₂ O ₃ , and ZrO ₂ , and
The content of the inorganic particles is a polymer-inorganic composite particle of 0.05 to 10% by weight based on the total weight of the polymer-inorganic composite particle. delete delete The polymer-inorganic composite particle of claim 1, wherein the average particle size (D ₅₀ ) of the polymer matrix is in the range of 1.5 to 2 μm. delete According to claim 1, wherein the near-infrared blocking inorganic particles are Au; Al ₂ O ₃ ; Al(OH) ₃ ; Ag; TiO ₂ containing aluminum hydroxide (Al(OH) ₃ -TiO ₂ ); And a polymer-inorganic composite particle, characterized in that at least one selected from the group consisting of TiO ₂ (Au-Al(OH) ₃ -TiO ₂ ) containing aluminum hydroxide and coated with gold nanoparticles on the surface. delete The method of claim 1, wherein the material of the polymer matrix is polymethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polyethyl methacrylate, polybutyl acrylate, Polybutyl methacrylate, polypentyl acrylate, polypentyl methacrylate, polyglycidyl methacrylate, polycyclohexyl acrylate, poly(2-ethylhexyl acrylate), polyacrylic acid and polymethacrylic acid, Polymer-inorganic composite particles, characterized in that selected from the group consisting of polystyrene, and copolymers thereof. a) forming a dispersion by dispersing inorganic particles in a mixture containing a monomer compound, a crosslinking agent, and a linear polymer having a molecular weight (M _w ) of 5000 to 350000, wherein the content of the linear polymer is 0.1 to 20% by weight based on the monomer compound Range;
b) adding an initiator to the dispersion; And
c) water to a dispersion of the initiator is added, containing the combination of a surfactant having a polymer stabilizer, 100 to 1,500 HLB value of the molecular weight (M _w) and 5 to 40 of having a 10,000 to 2,000,000 molecular weight (M _w) Contacting the solution to form an emulsion;
As a method for producing a polymer-inorganic composite particle comprising a,
The polymer-inorganic composite particles include a spherical polymer matrix having a size in the range of 1 to 3 µm to enable near-infrared blocking, and inorganic particles dispersed in the polymer matrix,
(i) In order to increase the near-infrared blocking effect of the polymer-inorganic composite particles, the inorganic particles have a size of 20 to 1000 nm and contain at least one metal element selected from the group consisting of Au, Al and Ag, or , or
(ii) In order to provide an effect of simultaneously blocking near-infrared rays and ultraviolet rays to the polymer-inorganic composite particles, the inorganic particles have a size of 20 to 100 nm, and TiO ₂ , ZnO, ZnO ₂ , CuO, CuO ₂ , Al At least one is selected from the group consisting of ₂ O ₃ , Al(OH) ₃ , CeO ₂ , Ce ₂ O ₃ , Fe ₂ O ₃ , and ZrO ₂ , and
A method for producing a polymer-inorganic composite particle, wherein the combination ratio of the polymer stabilizer and the surfactant is adjusted in the range of 1: 0.1 to 1.25 based on weight. The method of claim 9, wherein the temperature of the aqueous solution containing a combination of a polymer stabilizer and a surfactant in step c) is in the range of 50 to 100°C. delete The method of claim 9, wherein the linear polymer is polymethyl methacrylate, polystyrene, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polyethyl methacrylate, polybutyl acrylate, Polybutyl methacrylate, polypentyl acrylate, polypentyl methacrylate, polyglycidyl methacrylate, polycyclohexyl acrylate, poly(2-ethylhexyl acrylate), polyacrylic acid, polymethacrylic acid and Polymer-inorganic composite particles, characterized in that selected from the group consisting of a combination thereof. The method of claim 9, wherein the content of the inorganic particles in the dispersion is in the range of 0.05 to 10% by weight based on the total weight of the dispersion. The method of claim 9, wherein the monomer compound is methyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, Polymer-inorganic composite particles, characterized in that at least one selected from the group consisting of pentyl methacrylate, glycidyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl arylate, acrylic acid, methacrylic acid and styrene Method of manufacturing. delete The polymer-inorganic composite particle according to claim 9, wherein the weight ratio of the dispersion to which the initiator is added in step c): an aqueous solution containing a combination of a polymer stabilizer and a surfactant is in the range of 1:3 to 100. Method of manufacturing. The method of claim 9, wherein the surfactant is at least selected from the group consisting of a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a non-ionic surfactant. Method for producing a polymer-inorganic composite particle, characterized in that one. The method of claim 9, wherein the polymeric stabilizer is polyvinylalcohol (PVA), polyvinylpyrrolidone (PVP), polyvinyl acetate (PVAc), polyacrylic acid, and polyethylene oxide ( Polyethylene oxide; PEO), characterized in that at least one selected from the group consisting of polymer-inorganic composite particles. The method of claim 17, wherein the surfactant is sodium dodecyl sulfate (SDS), sodium lauryl ether sulfate (SLES), ammonium lauryl sulfate (ALS), cetyl trimethyl Ammonium bromide (cetyltrimethylammonium bromide; CTAB), dodecyl trimethylammonium bromide (dodecyltrimethylammonium bromide; DTAB), myristyl trimethylammonium bromide (TTAB) and at least one selected from the group consisting of polysorbate (Polysorbate) Method for producing a polymer-inorganic composite particle characterized by. A cosmetic composition comprising a polymer-inorganic composite particle according to any one of claims 1, 4, 6 and 8.

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