KR102484655B1 - Plate Shaped Zinc Oxide Particle, Preparation Method and Application Thereof - Google Patents

Abstract

The present invention relates to plate-shaped zinc oxide particles having an aspect ratio of 10:1 to 70:1, the ratio of average particle size to average particle thickness, and a particle size distribution d ₉₀ of 500 to 1500 nm, and a light beam comprising the plate-shaped zinc oxide particles. It relates to cosmetics for blocking, heat-dissipating and light blocking and/or preventing skin aging, antibacterial and/or antiviral agents containing plate-shaped zinc oxide particles, and a method for preparing the plate-shaped zinc oxide particles. The plate-shaped zinc oxide particles have excellent light and heat blocking properties, antiviral and antibacterial properties, and do not cause cloudiness. Therefore, the plate-shaped zinc oxide particles alone or in combination with other organic and/or inorganic materials can be used as functional materials for sunscreens, sunscreens, anti-skin aging cosmetics, antibacterial agents and/or antiviral agents.

Description

Plate Shaped Zinc Oxide Particle, Preparation Method and Application Thereof

The present invention relates to zinc oxide particles, and more particularly, to zinc oxide particles having excellent ultraviolet and heat blocking properties, antibacterial and antiviral properties, a method for preparing the zinc oxide particles, and industrial applications.

BACKGROUND As industrialization and urbanization progress, environmental pollution such as an increase in carbon gas emissions is caused, and the ozone layer in the atmosphere is seriously destroyed. Due to the destruction of the ozone layer, ultraviolet rays radiated from the sun to the earth are not sufficiently blocked by the ozone layer, and the human body is overexposed to ultraviolet rays. Skin aging and skin diseases such as skin cancer are increasing due to excessive exposure to ultraviolet rays, and accordingly, interest in sunscreens that can be applied to the human body is increasing.

Sunscreens used in cosmetics can be largely divided into organic sunscreens and inorganic sunscreens. Organic sunscreens are mainly composed of ultraviolet absorbers having a conjugation structure capable of absorbing ultraviolet rays in a molecular structure. However, organic sunscreens containing oxybenzone and octinoxate can not only react with the skin and cause skin irritation, but also seriously damage marine life, especially corals. However, its use is restricted in the US and Europe. Therefore, interest in inorganic sunscreens is increasing as an alternative to organic sunscreens. Inorganic sunscreens are metal oxides such as titanium oxide (TiO ₂ ), zinc oxide (ZnO) or cerium oxide (CeO ₂ ) having a high refractive index. powder is used. Unlike organic sunscreens that absorb ultraviolet rays and convert them into heat, inorganic sunscreens block ultraviolet rays through a mechanism that reflects and scatters them.

Compared to organic sunscreens, inorganic sunscreens not only have lower sunscreen effects, but also increase the content of inorganic sunscreens in cosmetics, resulting in instability in cosmetic formulations, whitening of the skin, and Skin application properties deteriorate. It is known that the stability of a cosmetic formulation may be adversely affected when a cosmetic containing an inorganic sunscreen is stored for a long period of time due to such degraded physical properties.

An object of the present invention is a metal oxide particle having excellent light blocking properties and heat blocking properties, low cloudiness and excellent skin application properties, a light blocking agent comprising the metal oxide particle, a heat dissipating agent, a light blocking agent, and/or It is intended to provide a cosmetic composition for preventing skin aging, an antibacterial agent and an antiviral agent.

Another object of the present invention is to provide a method for producing metal oxide particles having excellent physical properties.

In one aspect, it has an average particle size of 200 to 1200 nm and an average particle thickness of 10 to 100 nm, and an aspect ratio of the average particle size to the average particle thickness is 10:1 to 70:1, and the average particle thickness is 10:1 to 70:1. Platelet zinc oxide particles having a ratio of particle size distribution d ₉₀ to particle size (d ₉₀ /average particle size) of 1.0 to 3.5 are disclosed.

The average particle size may be 200 to 1100 nm, the average thickness may be 12.5 to 80 nm, and the ratio of d ₉₀ to the average particle size may be 1.05 to 2.00.

A particle size distribution d ₉₀ of the plate-like zinc oxide particles may be 600 nm to 3000 nm.

Optionally, the ratio of d _[4,3] , which is the average diameter calculated from the volume of the plate-like zinc oxide particles, to the average particle size (d _[4,3] /average particle size) may be 0.3 to 2.0.

In addition, the ratio of the peak intensity in the wavelength range of 500 to 1000 nm to the peak intensity in the wavelength range of 300 to 400 nm in the photoluminescence spectrum of the plate-like zinc oxide particles may be 0.1 to 1.5. .

Optionally, the plate-shaped zinc oxide particles may be surface treated.

In another aspect, a sunscreen comprising the above-described plate-like zinc oxide particles is disclosed.

In another aspect, a heat dissipating agent comprising the above-described planar zinc oxide particles is disclosed.

Optionally, the light blocking agent and/or the heat dissipating agent may further include inorganic particles other than plate-like zinc oxide particles.

For example, the inorganic particles may be selected from the group consisting of titanium oxide particles, zinc oxide particles, and combinations thereof.

For example, the planar zinc oxide particles and the inorganic particles may be mixed in a weight ratio of 1:1 to 10:1 in a light blocking agent and/or a heat dissipating agent.

In another aspect, a cosmetic composition for sunscreen or skin aging prevention comprising the above-described plate-like zinc oxide particles as an active ingredient is disclosed.

For example, the plate-like zinc oxide particles may be included in an amount of 5 to 20% by weight in the cosmetic composition.

Optionally, the cosmetic composition may further include other inorganic particles in addition to the plate-shaped zinc oxide particles. In this case, the content of the plate-shaped zinc oxide particles and the inorganic particles may be 5 to 20% by weight with respect to the total amount of the cosmetic composition.

In another aspect, an antibacterial composition and/or an antiviral composition comprising the plate-like zinc oxide particles as an active ingredient is disclosed.

In one aspect, in the antibacterial agent and/or antiviral agent, the planar zinc oxide particles may be present in a form dispersed in a binder.

In an optional aspect, the antibacterial agent and/or antiviral agent may be formulated in the form of a film, and the plate-shaped zinc oxide particles may be dispersed in the film.

In another aspect, discharging a zinc air battery to obtain an electrolyte solution containing an anionic zinc compound and zinc oxide; diluting the electrolyte solution by adding a diluting solvent to the obtained solution; and forming zinc oxide crystals by reacting a zinc salt with the diluted electrolyte.

At this time, the plate-shaped zinc oxide particles have an average particle size of 200 to 1200 nm and an average particle thickness of 10 to 80 nm, and the aspect ratio of the average particle size to the average particle thickness is 10: 1 to 70: 1, and the ratio of the particle size distribution d ₉₀ of the particles to the average particle size (d ₉₀ /average particle size) may be 1.0 to 3.5.

For example, the forming of the zinc oxide crystals may be performed in the presence of a salt.

In an optional aspect, a step of adding a salt to the diluted electrolyte solution may be further included between the step of diluting the electrolyte solution and the step of forming the zinc oxide crystals.

The salt may be selected from the group consisting of C _{1 -C 10 organic acid salts of alkali metals, C 1 -C 10 organic acid} salts of alkaline earth metals, and combinations thereof.

The zinc salt may be selected from the group consisting of organic zinc, inorganic zinc, and combinations thereof.

In this case, the organic acid constituting the zinc salt may be a C ₁ -C ₂₀ organic acid, and the inorganic acid constituting the zinc salt may be selected from the group consisting of nitric acid, sulfuric acid, and hydrochloric acid.

In an optional aspect, after the step of forming the zinc oxide crystals, a step of surface treating the synthesized plate-like zinc oxide crystals may be further included.

The planar zinc oxide particles of the present invention have a high aspect ratio defined as the average size of the particles to the average thickness of the particles, and the primary particles are not agglomerated. The plate-shaped zinc oxide particles of the present invention are excellent in UV and heat blocking effects and skin application properties, and have little cloudiness. Therefore, compositions such as sunscreens or cosmetics may contain a higher content of the plate-like zinc oxide particles according to the present invention than conventional inorganic particles.

In addition, if necessary, it can be combined with other inorganic particles having an appropriate particle size to realize a high UV blocking rate and heat blocking effect similar to that of organic rP sunscreens. The plate-shaped zinc oxide particles according to the present invention can be used as a material for cosmetics for preventing skin aging as well as for sunscreen and sunscreen cosmetics. It can be used as a functional material for cosmetics to realize excellent application properties and formulation stability.

In addition, since the plate-like zinc oxide particles have almost no defect sites, they are very stable. It kills bacteria and/or viruses, such as gram-positive and gram-negative bacteria. Therefore, the plate-shaped zinc oxide particles can be applied as an active ingredient of antibacterial and/or antiviral agents.

In addition, since the plate-like zinc oxide particles of the present invention can be synthesized from an electrolyte solution produced by charging a zinc-air battery, it has an advantage of being produced in an environmentally friendly manner.

1 is a schematic diagram schematically showing the shape and growth direction of plate-like zinc oxide particles according to the present invention.
2 is a flow chart schematically showing a process for producing plate-like zinc oxide particles according to the present invention.
3 is a schematic diagram schematically showing the configuration of a zinc air battery system applied to obtain an anionic zinc compound according to the present invention.
4 to 48 are scanning electron microscope (SEM) photographs of plate-shaped zinc oxide particles synthesized according to an exemplary embodiment of the present invention, zinc oxide particles synthesized according to a comparative example, and commercially available inorganic oxide particles, respectively. , It is a graph measuring the particle size distribution for each inorganic oxide particle.
49 is a graph showing the results of measuring photoluminescence spectra of plate-like zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic oxide particles.
50 is a graph showing the results of measuring the light transmittance of cosmetics formulated to contain 15% by weight of plate-like zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles in single particles, respectively. .
51 shows the results of measuring color change and temperature change rate of cosmetics formulated to contain 15% by weight of plate-shaped zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles, respectively, in a single particle. it's a graph
52 is a photograph of cosmetics formulated to contain 15% by weight of plate-like zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles in a single particle, one week after formulation. It's a video.
53 is a graph showing the results of measuring the UV blocking rate and temperature change rate of cosmetics formulated by varying the blending ratio of plate-shaped zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles.
54 is a graph showing the results of measuring color change of cosmetics formulated by varying the blending ratio of plate-like zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles.
55 is a photograph taken after one week of cosmetics formulated with different blending ratios of plate-shaped zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles.
56 is a graph showing the results of measuring the UV blocking rate and temperature change rate of cosmetics formulated with different mixing ratios of plate-shaped zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles.
57 is a graph showing the results of measuring color change of cosmetics formulated by varying the blending ratio of plate-like zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles.
58 is a photograph taken one week after cosmetics formulated by varying the blending ratio of plate-shaped zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles.
59 is a graph showing the relationship between the chromaticity value and the temperature change rate of cosmetics formulated by varying the blending ratio of plate-like zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles.
60 is a graph showing the results of measuring the UV blocking rate and temperature change rate of cosmetics formulated with different mixing ratios of plate-like zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles.
61 is a graph showing the results of measuring color change of cosmetics formulated by varying the blending ratio of plate-shaped zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles.
62 is a photograph taken one week after cosmetics formulated with different blending ratios of plate-shaped zinc oxide particles synthesized according to an exemplary embodiment of the present invention and commercially available inorganic particles.
63 and 64 show the results of inoculating a formulated film coated with plate-like zinc oxide particles synthesized according to an exemplary embodiment of the present invention with a virus, and measuring antiviral activity over time after inoculation. graphs and pictures

Hereinafter, the present invention will be described with reference to the accompanying drawings when necessary.

[Zinc oxide particles]

면(120)은 각각 판상 산화아연 입자(100)를 구성하는 금속 양이온인 Zn²⁺와 음이온인 O^2-가 분포하는 극성 면(polar plane)이다. 한편, 이들 극성 면(110, 120)에 대하여 실질적으로 직교하는

면(130) 및

면(140) 등이 형성된다. 판상 산화아연 입자(100)는 극성 면(110, 120)에 대하여 수직하게 형성되는 면, 예를 들어

면(130)을 따라 결정이 길게 성장한다. 반면, 판상 산화아연 입자(100)의 극성 면인 [0001]면(110)과

면(120)으로의 결정 성장은 억제된다. The plate-like zinc oxide particles according to the present invention have a plate-like structure and a controlled average particle size, aspect ratio, and particle size distribution, and thus have good ultraviolet and heat blocking performance as well as good formulation characteristics. 1 is a schematic diagram schematically showing the shape of plate-shaped zinc oxide particles prepared according to the present invention. The plate-like zinc oxide particle 100 according to the present invention may have a flat hexagonal column shape. The [0001] facet 110 of the plate-like zinc oxide particle 100 and the opposite side of the [0001] facet 110

The surface 120 is a polar plane in which Zn ²⁺ , which is a metal cation, and O ^2- , which is an anion, respectively constituting the plate-shaped zinc oxide particle 100 , are distributed. On the other hand, substantially orthogonal to these polar faces (110, 120)

cotton 130 and

Face 140 and the like are formed. The plate-shaped zinc oxide particles 100 are formed perpendicularly to the polar surfaces 110 and 120, for example,

Crystals grow elongated along face 130 . On the other hand, the [0001] surface 110, which is the polar surface of the plate-like zinc oxide particle 100,

Crystal growth into face 120 is inhibited.

면(120) 사이의 평균 두께(T)는 10 내지 100 nm, 예를 들어, 15 내지 80 nm, 선택적으로는 15 내지 70 nm를 갖는다. 이에 따라, 판상 산화아연 입자(100)의 평균 입자 두께(T)에 대한 평균 입자 크기(S)의 종횡비(aspect ratio)는 10:1 내지 70:1, 예를 들어, 10:1 내지 50:1을 갖는다. The plate-like zinc oxide particles 100 may have an average particle size (S), that is, an average length of a [0110] plane in a crystal growth direction of 200 to 1200 nm, for example, 300 to 1100 nm. In addition, the zinc oxide particle 100 of the present invention has an average particle thickness (T), that is, the polar surface [0001] surface 110 and

The average thickness T between faces 120 is between 10 and 100 nm, for example between 15 and 80 nm, optionally between 15 and 70 nm. Accordingly, the aspect ratio of the average particle size (S) to the average particle thickness (T) of the plate-like zinc oxide particles 100 is 10:1 to 70:1, for example, 10:1 to 50: have 1

In this specification, "average particle size" means the length of the largest side among the three sides (horizontal length, vertical length and thickness) constituting the plate-shaped particles. In the present specification, "aspect ratio" may be defined as the ratio of the length of the largest side and the thickness of the shortest side among the three sides constituting the plate-shaped particle.

면(130)을 따라 결정이 성장하기 때문에, 극성 면인 [0001]면(110)과

면(120)의 비표면적이 매우 넓다. reflecting mirror plane인 [0001]면(110)과

면(120) 사이에서 polariton lasing을 통해 생성된 stimulated emission이 증폭되어, 금속 양이온인 아연 성분이 분포하는 [0001]면(110)을 통해 외부의 빛이 판상 산화아연 입자(100)의 결정 내부로 입사되고, [0001]면(110)을 통해 외부로 방출된다. Platelet zinc oxide particles 100 having a very flat hexagonal plate shape are mainly

Since the crystal grows along the face 130, the [0001] face 110 and the polar face

The specific surface area of the surface 120 is very large. The [0001] plane 110, which is a reflecting mirror plane, and

The stimulated emission generated through polariton lasing between the surfaces 120 is amplified, and external light passes through the surface 110 where the zinc component, which is a metal cation, is distributed to the inside of the crystal of the plate-like zinc oxide particle 100 It is incident and emitted to the outside through the [0001] plane 110.

That is, the [0001] surface 110, which is one polar surface of the plate-shaped zinc oxide particle 100, is a surface on which external light is incident, and may serve as a reflecting mirror plane for generated stimulated emission. In addition, the peak intensity of the photoluminescence (PL) spectrum of the plate-like zinc oxide particles 100 and defects such as oxygen vacancies on the surface of the plate-like zinc oxide particles 100 are greatly reduced. .

면(120)의 비표면적이 극대화된 판상 산화아연 입자(100)는 자외선은 물론이고, 가시광선 및 적외선을 효율적으로 차단할 수 있고, 열 차단 효과가 극대화될 수 있다. 아울러, 물리적 특성이 변화된 판상 산화아연 입자(100)는 향상된 항균 특성 및/또는 항바이러스 특성을 갖는다. The [0001] plane (110), which is a polar plane, and

The plate-shaped zinc oxide particle 100 having a maximized specific surface area of the surface 120 can efficiently block ultraviolet rays as well as visible and infrared rays, and the heat blocking effect can be maximized. In addition, the plate-shaped zinc oxide particles 100 having changed physical properties have improved antibacterial and/or antiviral properties.

The plate-shaped zinc oxide particles 100 may have a specific particle size distribution by controlling aggregation or agglomeration of primary particles. As used herein, the terms particle size distribution d ₁₀ , d ₅₀ and d ₉₀ refer to 10% cumulative particle size, 50% cumulative particle size and 90% cumulative particle size by volume, respectively, and d[4,3] is It means the average size calculated from the volume of the particles, that is, the average size of particles having the same volume as the actual particles.

In an exemplary aspect, the ratio of d ₉₀ , which is the particle size distribution of the 90% cumulative particle size to the average particle size S of the platelet zinc oxide particles 100 (d ₉₀ /average particle size), is 1.0 to 3.5, for example , 1.05 to 2.00, optionally 1.05 to 1.50. For example, the particle size distribution d ₉₀ of the zinc oxide particles 100 may be 600 to 2000 nm, eg 600 to 1500 nm, optionally 650 to 1400 nm.

In another exemplary aspect, the plate-like zinc oxide particles 100 have a ratio of d _[4,3] , which is the average diameter calculated from the volume of the plate-like zinc oxide particles 100, to the average particle size (S) (d _{[4 ,3]} /average particle size) may be from 0.3 to 2.0, such as from 0.3 to 1.5, optionally from 0.35 to 1.5 (eg from 0.35 to 1.0). For example, d[ _4,3 ] of the plate-shaped zinc oxide particles 100 may be 250 to 650 nm, preferably 300 to 600 nm, but is not limited thereto.

면(120)의 비표면적이 넓어지고, 판상 산화아연 입자(100) 표면에서 산소 빈격자점과 같은 결함이 크게 감소한다. As described above, the aspect ratio of the plate-shaped zinc oxide particles 100, which is the ratio between the average particle size (S) and the average particle thickness (T), is very high. The [0001] plane 110, which is the polar plane of the plate-shaped zinc oxide particle 100, and

The specific surface area of the surface 120 is increased, and defects such as oxygen vacancy points on the surface of the plate-like zinc oxide particle 100 are greatly reduced.

The peak intensity of the plate-shaped zinc oxide particles 100 increases in the ultraviolet wavelength range of 300 to 400 nm, which is a unique emission wavelength range, while the peak intensity decreases significantly in the wavelength range of 500 to 1000 nm. For example, in the photoluminescence (PL) spectrum of the plate-shaped zinc oxide particles 100, the ratio of the peak intensity in the wavelength range of 300 to 400 nm and the peak intensity in the wavelength range of 500 to 1000 nm is 0.1 to 1.5, For example, it may be 0.15 to 1.2.

In an optional aspect, the planar zinc oxide particles 100 may be coated with a surface treatment agent. The surface treatment agent includes, but is not particularly limited to, silicon oxide (silica), silicone oil, organic silicon compounds, organic titanium compounds, and combinations thereof.

Silicone oil is triethoxycaprylsilane, methylhydrogenpolysiloxane, dimethylpolysiloxane-methylhydrogenpolysiloxane copolymer triethoxysilylethylpolydimethylsiloxyethyldimethicone, triethoxysilylethylpolydimethylsiloxyethylhexyldimethicone , It may be selected from the group consisting of acrylic silicone resins and combinations thereof, but is not limited thereto.

The organosilicon compound may include a silane coupling agent and/or an alkoxy silane. The silane coupling agent and alkoxy silane may each have 2 to 4 hydrolyzable functional groups, alkoxy groups.

Illustratively, the silane coupling agent is (3-acryloxypropyl)trimethoxysilane (APTMS), methacryloxymethyltriethoxysilane (MMS), 3-methacryloxypropyltrimethoxysilane (MPTMS), 3 - (meth)acryloyl group-containing silane coupling agents such as methacryloxypropyltriethoxysilane (MPTES) and (3-acryloxypropyl)methyldimethoxysilane (APDMS); 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane (APTES), 3-(2-aminoethylamino)propyltrimethoxysilane (AEAPTMS), 3-(2-aminoethyl amino group-containing silane coupling agents such as amino)propylmethyldimethoxysilane, [3-(phenylamino)propyl]trimethoxysilane (PAPTMS), 3-aminopropyl(methyl)diethoxysilane (APPDES); 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane (ECETMS), 3-glycidyloxypropyltrimethoxysilane (GPTEMS), 3-glycidyloxypropyltriethoxysilane (GPTEOS), silane coupling agents containing an epoxy group or glycidyl group such as 3-glycidoxypropyl (methyl) dimethoxysilane (GPMDMS) and 3-glycidoxypropyl (methyl) diethoxysilane (GPMDES); vinyl group-containing silane coupling agents such as vinyltrimethoxysilane (VTMS), vinyltriethoxysilane (VTES), vinyltris(methoxyethoxy)silane, and methyl(vinyl)diethoxysilane (MVDES); mercapto group-containing silane coupling agents such as 3-mercaptopropyltriethoxysilane (MPTES); sulfide-containing silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide (TESPT); silane coupling agents containing isocyanate groups such as 3-isocyanatopropyltriethoxysilane (ICPTES) and combinations thereof.

Alkoxy silanes include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, tetraethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxy Silane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, phenyltrimethoxysilane, methyl(phenyl)diethoxysilane, diphenyldimethoxysilane, phenyl triethoxysilane, (4-chlorophenyl)triethoxysilane, and combinations thereof.

Organic titanium compounds include di-i-propoxytitanium bis(methylacetoacetate), di-i-propoxytitanium bis(ethylacetoacetate), di-i-propoxytitanium bis(propylacetoacetate), di-i- Propoxytitanium bis(butyl acetoacetate), di-i-propoxytitanium bis(hexylacetoacetate), di-n-propoxytitanium bis(methylacetoacetate), di-n-propoxytitanium bis(ethylacetoacetate) , di-n-propoxytitanium bis (propylacetoacetate), di-n-propoxytitanium bis (butylacetoacetate), di-n-propoxytitanium bis (hexylacetoacetate), di-n-butoxy Titanium bis (methylacetoacetate), di-n-butoxytitanium bis (ethylacetoacetate), di-n-butoxytitanium bis (propylacetoacetate), di-n-butoxytitanium bis (butylacetoacetate), Di-n-butoxytitanium bis (hexylacetoacetate), di-i-propoxytitanium bis (acetylacetonate), di-n-propoxytitanium bis (acetylacetonate), di-n-butoxytitanium bis (acetylacetonate), di-i-propoxytitanium bis(triethanolaminate), di-i-propoxytitaniumbis(diethanolaminate), dibutoxytitaniumbis(triethanolaminate), dibutoxytitaniumbis( diethanolamine), dioctyloxytitanium bis(octylene glycolate), dihydroxytitanium bislactate, triisostearoyloxy-isopropoxytitanium, and combinations thereof, but is not limited thereto. don't

The surface treatment method is not particularly limited, and the surface treatment may be performed with a surface treatment agent in an amount of about 0.1 to 20% by weight based on the total amount of the plate-shaped zinc oxide particles 100 to be surface treated.

The plate-like zinc oxide particles 100 not only have a hexagonal plate-like shape with a very high aspect ratio, but also suppress aggregation of primary particles. The shape and size distribution of the particles are controlled, and surface defects such as oxygen vacancy points are minimized. The plate-shaped zinc oxide particles maximize light blocking effect and heat blocking effect, and can implement excellent antibacterial and/or antiviral properties. In addition, as will be described later, when used as a sunscreen, sunscreen, and/or anti-aging cosmetics, there is little whitening, and the stability and application properties of the formulation are improved.

[Method for producing plate-shaped zinc oxide particles]

2 is a flow chart schematically showing a process for producing plate-like zinc oxide particles according to the present invention. As shown in FIG. 2, the process for producing plate-like zinc oxide particles includes discharging a zinc-air battery to obtain an electrolyte containing an anionic zinc compound (step S210), diluting the obtained electrolyte (step S220), Adding and reacting a zinc salt to the electrolyte containing the obtained anionic zinc compound to synthesize plate-like zinc oxide particles (step S230), filtering and/or washing the product containing the synthesized plate-like zinc oxide particles as necessary Step (S240), heat treatment or drying of the synthesized plate-like zinc oxide particles to grow plate-like zinc oxide particles (step S250), and treatment of the surface of the plate-like zinc oxide particles (step S260).

The zinc air battery is discharged to obtain an electrolyte containing an anionic zinc compound that can be converted into zinc oxide particles (step S210). 3 is a schematic diagram schematically showing the configuration of a zinc-known battery system applied to obtain an electrolyte containing an anionic zinc compound according to the present invention. As shown in FIG. 3, the zinc air battery system 200 for obtaining an anionic zinc compound has a negative electrode 210 as a first electrode, a positive electrode 220 as a second electrode, and between two electrodes 210 and 220. It includes a separator 240 positioned between the disposed electrolyte 230 and the two electrodes 210 and 220.

The negative electrode 210 releases zinc ions when the zinc air battery system 200 is discharged and absorbs zinc ions when the zinc air battery system 200 is charged. In relation to this function, the negative electrode 210 may include a current collecting layer 212 for collecting the negative electrode and a negative active material layer 214 provided on the negative electrode current collector 212. can Any material having conductivity may be used for the anode current collector 212 . For example, the anode current collector 212 may include a material to which zinc or zinc alloy used as the anode active material layer 214 is easily attached. there is.

For example, the negative current collector 212 may be made of aluminum (Al), nickel (Ni), iron (Fe), stainless steel, copper (Cu), copper-zinc alloy (Cu-Zn alloy, brass), titanium (Ti) And it may be made of a conductive material selected from the group consisting of metal materials, carbon materials, and combinations thereof, such as combinations thereof, but is not limited thereto. The carbon material is a conductive carbon material, and may include, for example, a porous carbon material. For example, porous carbon materials include graphite (graphite), grapheme, fullerene, carbon nano-tube (CNT), carbon fiber, carbon black, activated carbon, and combinations thereof. However, the material of the negative electrode current collector 212 is not limited to these materials. Non-limiting examples of carbon black may be acetylene black, denca black, ketjen black, carbon black, and combinations thereof.

In an exemplary embodiment, the anode current collector 212 may use a carbon-coated aluminum material. The carbon-coated aluminum material has advantages such as excellent adhesion, low contact resistance, and prevention of corrosion of aluminum by polysulfide. If necessary, the anode current collector 212 may have various forms such as a film, sheet, foil, net, porous material, foam or nonwoven material.

The negative electrode active material layer 214 uses metal zinc alone, a zinc-aluminum (Zn-Al) alloy, a zinc-tin (Zn-Sn) alloy, and/or a zinc-aluminum-tin (Zn-Al-Sn) alloy. It may be selected from the group consisting of zinc-metal alloys and blends, such as, but is not limited thereto. For example, when the negative active material layer 214 in the form of an alloy or blend with other metals is adopted, the zinc component is 90 to 99% by weight, preferably 93 to 99% by weight, of the total metal active material layer 214, More preferably 95 to 99% by weight (for example, 95.5 to 99% by weight, 95 to 97% by weight or 95.5 to 97% by weight), and the other metal component is 1 to 10% by weight, preferably 1 to 7% by weight. % by weight, more preferably 1 to 5% by weight (eg, 1 to 4.5% by weight, 3 to 5% by weight or 3 to 4.5% by weight). Zinc and/or zinc alloy as a component of the negative electrode active material layer 214 has a high theoretical energy density of 820 mAh/g.

At this time, the metal material constituting the negative electrode active material layer 214 may have a powder type, plate type, granule type, or mesh type, but is not limited thereto. In order to attach the negative electrode active material layer 214 to the negative electrode current collector 212, a dipping method, an electrodeposition method (acid/alkaline method), or a casting in which the negative electrode active material is manufactured into a plate-shaped negative electrode using a roller or casting A method (die casting method) may be applied, but is not limited thereto.

The positive electrode 220 may reduce oxygen during discharging and release oxygen during charging. For example, the cathode 220 includes a cathode current collector 222 for current collection and a cathode active material layer 224 provided on the cathode current collector 222 . The positive current collector 222 is for collecting the positive electrode 220 and may be made of any material having conductivity. For example, the cathode current collector 222 may include a metal material such as aluminum (Al), nickel (Ni), iron (Fe), copper (Cu), stainless steel, titanium (Ti), and a combination thereof, a carbon material, and a combination thereof. It may be made of a conductive material selected from the group consisting of combinations.

The carbon material is a conductive carbon material, and may include, for example, a porous carbon material. The porous carbon material may be selected from the group consisting of graphite (graphite), graphene, fullerene, carbon nanotube (CNT), carbon fiber, carbon black, activated carbon, and combinations thereof, but the positive electrode current collector 220 It is not limited to these porous carbon materials. Non-limiting examples of carbon black may be acetylene black, Denka black, Ketjen black, carbon black, and combinations thereof. Oxygen in the air may be used as a reactive material for the cathode active material layer 224 .

For example, a carbon-coated aluminum current collector may be used as the cathode current collector 222 . When a carbon-coated aluminum current collector is used as the positive electrode current collector 222, the adhesion to the active material is excellent, the contact resistance is low, and corrosion of aluminum by polysulfide can be prevented compared to a carbon-coated aluminum current collector. There are advantages to being able to The cathode current collector 222 may have various forms such as a film, sheet, foil, net, porous material, foam, or nonwoven material.

In an alternative embodiment, the positive electrode 220 is a catalytically active layer composed of one or more oxygen reduction catalysts between the positive electrode current collector 222 and the positive electrode active material layer 224 to promote the oxygen reaction in the air. layer) may be further included. In this case, the outside of the cathode active material layer 224 may have a structure of a catalytic active layer-anode current collector, or a structure of a first catalytic active layer-first cathode current collector-second catalytic active layer-second cathode current collector. there is. Non-limiting examples of the oxygen reduction catalyst may be selected from the group consisting of noble metals, nonmetals, metal oxides, organic metal complexes, resins, and combinations thereof, but are not limited thereto.

The noble metal constituting the oxygen reduction catalyst may be selected from the group consisting of platinum (Pt), gold (Au) and/or silver (Ag). The non-metal constituting the oxygen reduction catalyst may be selected from the group consisting of boron (B), nitrogen (N) and/or sulfur (S). The metal oxide constituting the oxygen reduction catalyst may be a metal oxide selected from the group consisting of manganese (Mn), nickel (Ni), and/or cobalt (Co). The organometallic complex constituting the oxygen reduction catalyst may be selected from the group consisting of metal porphyrin and/or metal phthalocyanine. The resin constituting the oxygen reduction catalyst includes polytetrafluoroethylene such as Teflon. However, noble metals, nonmetals, metal oxides, organic metal complexes, and resins constituting the oxygen reduction catalyst are not limited to the above materials.

In a non-limiting exemplary embodiment, the oxygen reduction catalyst may be 0.1 to 10 weight percent of the total composition of the anode 220. If the content of the oxygen reduction catalyst is less than 0.1% by weight, it is not sufficient to promote the oxygen reaction, and if it exceeds 10% by weight, the degree of dispersion may decrease, and the oxygen reaction is no longer promoted, increasing the manufacturing cost of the zinc oxide battery can do.

In addition, in addition to the oxygen reduction catalyst, the positive electrode 220 optionally includes a conductive material and a binder and/or a solvent for well attaching oxygen, which is the positive electrode active material provided to the positive electrode active material layer 224, to the positive electrode current collector 222. may include more. The conductive material is not particularly limited as long as it does not cause chemical change in the zinc air battery. For example, as the conductive material, carbon material, conductive polymer, conductive fiber, and/or metal powder may be used.

As an example of the conductive material, any carbon material may be used as long as it has a porous structure or has a high specific surface area. For example, the carbon material may be a material selected from the group consisting of mesoporous carbon, graphite, graphene, carbon nanotube, carbon fiber, fullerene, carbon black, activated carbon, and combinations thereof. may, but is not limited thereto. Conductive polymers, which are examples of conductive materials, include (poly)aniline (PANI), (poly)thiophene, (poly)pyrrole, (poly)acetylene, and combinations thereof. can be used Carbon fiber or metal fiber may be used as the conductive fiber, which is an example of the conductive material, and fluorocarbon, aluminum, and/or nickel powder may be used as the metal powder. However, the conductive material that can be used according to the present invention is not limited to the above-mentioned material.

For example, the content of the conductive material may be 10% to 99% by weight based on the total weight of the positive electrode 220 . If the content of the conductive material is less than 10% by weight, the reaction site may decrease and the battery capacity of the zinc air battery may decrease. If the content of the conductive material exceeds 99% by weight, the oxygen reduction catalyst relatively occupies Since the content is reduced, the promotion of the oxygen reaction may not be performed smoothly.

The binder is poly(vinyl acetate), polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, crosslinked polyethylene oxide, polyvinyl ether, poly(methyl methacrylate), polyvinylidene fluoride, Copolymers of polyhexafluoropropylene and polyvinylidene fluoride, poly(ethyl acrylate), polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinylpyridine, polystyrene, derivatives thereof, blends thereof (blend) and / or may be selected from the group consisting of copolymers thereof.

The content of the binder may be added in an amount of 0.5 wt% to 30 wt% based on the total weight of the mixture including the cathode active material. If the content of the binder is less than 0.5% by weight, the physical properties of the positive electrode 220 may deteriorate and the active material and the conductive material in the positive electrode 220 may be eliminated. If the content exceeds 30% by weight, the ratio of the active material and the conductive material in the positive electrode 220 As this is relatively reduced, the battery capacity may decrease.

The solvent may use a solvent having a boiling point of 200 ° C or less, for example, acetonitrile, methanol, ethanol, tetrahydrofuran, water, isopropyl alcohol, acetone, N, N-dimethylformamide (DMF) and / Alternatively, a solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP) may be used, but is not limited thereto.

In addition, according to an exemplary embodiment of the present invention, the known zinc battery system 200, which can be adopted to obtain and produce an electrolyte containing an anionic zinc compound, is an electrolyte solution supplied between the negative electrode 210 and the positive electrode 220. (230) and a separator (240). The electrolyte solution 230 may include water and an electrolyte salt that is dissociated into water and changed into an ionic state. A non-limiting example of the electrolyte salt is a hydroxide of an alkali metal or an alkaline earth metal. Specifically, as an electrolyte salt that can be used, an alkali metal hydroxide such as potassium hydroxide (KOH) and/or sodium hydroxide (NaOH) may be used. As these electrolyte salts are dissociated in water, hydroxide ions (OH ^- ) are dissolved and can be used as an electrolyte solution.

The separator 240 positioned between the cathode 210 and the anode 220 separates or insulates the cathode 210 and the anode 220 from each other, and enables zinc ion transport between the anode 210 and the anode 220. As long as it allows only zinc ions to pass through and blocks the rest, any one can be used. For example, the separator 240 may be made of a porous non-conductive or insulating material. More specifically, the separator 240 may be a polymer non-woven fabric such as a polypropylene non-woven fabric or a polyphenylene sulfide non-woven fabric; and/or a porous film of an olefinic resin such as polyethylene or polypropylene.

The shape of the zinc air battery system 200 is not limited, and may be illustratively a flat plate shape, a cylindrical shape, a sheet shape, a laminated shape, a horn shape, or a coin shape. In the zinc air battery system 200, different reactions are induced according to charging and discharging of the battery, so that an anionic zinc compound and zinc oxide can be obtained. According to an exemplary embodiment of the present invention, the anionic zinc compound is a zinc air battery system using an electrode (for example, a negative electrode) of a zinc air battery composed of metal zinc or an alloy of metal zinc and another metal, and an air positive electrode and an electrolyte solution. It may be a mixture of ionized hydroxide ions remaining in the basic electrolyte during the charging process of (200).

For example, in the case of the zinc air battery system 200 using an alkali metal hydroxide and/or an alkaline earth metal hydroxide as an electrolyte salt, zinc hydroxide ions ( Zn(OH ₄ ) ^2- ) is generated, and in the electrolyte 230, zinc hydroxide ions generated in the anode 210 are decomposed to produce zinc oxide (ZnO).

Anode: Zn + 4 OH ^- → Zn(OH) ₄ ^2- + 2e ^- (1)

Electrolyte (Fluid): Zn(OH) ₄ ^2- → ZnO + H ₂ O + 2OH ^- (2)

For example, an electrolyte salt containing an alkali metal hydroxide and/or an alkaline earth metal hydroxide may be used at a concentration of 30 to 60% (w/v), preferably 40 to 50% (w/v) in the electrolyte solution 230. can In this case, the pH of the electrolyte 230 may be approximately 9 to 13, preferably 10 to 12, and the specific gravity of the electrolyte may be approximately 1.30 to 1.70 g/mL. If the concentration of the electrolyte salt in the electrolyte solution 230 is less than the above range, the pH of the electrolyte solution 230 constituting the zinc air battery system 200 is less than a desired level, so that charging may not occur smoothly, and the concentration of the electrolyte salt may not If the range is exceeded, there is a concern that the anionic zinc compound remaining in the electrolyte solution 230 due to the discharge of the zinc air battery system 200 may be excessively increased.

According to an exemplary embodiment, when it is desired to obtain an anionic zinc compound in the electrolyte 230 by discharging the zinc air battery system 200, a current of about 1 to 5 A may be applied to the zinc air battery system 200. and apply current for about 5 to 15 hours. Accordingly, when the zinc air battery system 200 is discharged, a voltage of about 0.7 to 1.1 V is generated and has an average battery capacity of about 20 to 24 Ah. When the applied current is less than 1 A, the battery is not sufficiently charged, so it may be difficult to sufficiently obtain an anionic zinc compound in the electrolyte 230. Anions remaining in the electrolyte 230 even when the applied current exceeds 5 A Zinc compounds may no longer increase proportionally.

면(120)에 분포하는 O^2- site로 반응하기 어렵다. 따라서, 전해액(230)에 잔류하는 수산화아연 이온은 생성된 산화아연 결정 중에서 비극성 평면인

면(130)으로 반응하고, 최종적으로 산화아연 결정은

(130)을 따라 길게 성장하여, 높은 종횡비를 갖는 판상 산화아연 입자(100)를 제조할 수 있다. As can be seen from the above reaction formula (1) and reaction formula (2), by the discharge of the zinc air battery system 200, zinc oxide molecules and zinc hydroxide ions (Zn(OH ₄ ), which are anionic zinc compounds, are formed inside the electrolyte solution 230) ₂ ^- ) is present in significant amounts. At this time, the zinc hydroxide ions remaining in the electrolyte 230 are negatively charged among the generated zinc oxide crystals.

It is difficult to react with the O ^2- site distributed on the surface 120. Therefore, zinc hydroxide ions remaining in the electrolyte solution 230 are non-polar planes among the generated zinc oxide crystals.

Reacts with the surface 130, and finally the zinc oxide crystal

By growing elongately along 130, plate-like zinc oxide particles 100 having a high aspect ratio can be produced.

Through the discharge of the zinc air battery system 200, the electrolyte solution 230 including zinc oxide and an anionic zinc compound may be diluted (step S220). The dilution solvent is not particularly limited, and distilled water may be used as an example. In this case, the diluted solvent may be used in a volume 10 to 50 times the volume of the recovered electrolyte solution 230 .

Optionally, the diluting solvent may be an electrolyte solution containing an electrolyte having a lower concentration than the electrolyte solution obtained through discharging of the zinc air battery system 200 . In this case, the content of the electrolyte contained in the electrolyte solution (mother solution) included before dilution may be approximately 1 to 10%, for example, 2 to 5% of the total electrolyte content contained in the electrolyte solution 230 after dilution.

In one example, the electrolyte solution containing zinc oxide and an anionic compound using a diluting solvent is finally 2 to 10% (w / v), for example 3 to 8% (w / v), optionally 4 to 7% ( w/v) of the electrolyte. When the concentration of the electrolyte is adjusted within the above range, zinc oxide particles 100 having controlled size and particle size distribution may be manufactured in a subsequent process.

When the concentration of the electrolyte in the electrolyte 230 is less than 2% (w/v), the average size of the primary zinc oxide particles 100 may exceed 1200 nm, and the concentration of the electrolyte in the electrolyte 230 is 10% (w/v). /v), the average size of the primary zinc oxide particles 100 becomes less than 200 nm, and plate-shaped zinc oxide particles 100 having a desired size and particle size distribution may not be obtained.

면(130)으로 성장하는데 필요한 소스로 사용될 수 있다. The anionic zinc compound remaining in the diluted electrolyte solution 230 serves as a seed for growth of the plate-like zinc oxide particles 100, and the electrolyte solution included in the additionally added low-concentration electrolyte dilution solvent (eg, KOH ) is that the plate-like zinc oxide particles 100

It can be used as a source needed to grow to the surface 130.

면(130)을 따라 분포하기 때문에, 음이온 아연 화합물과 첨가된 아연 염의 반응에 의하여 형성되는 산화아연 결정은 비극성 표면인

면(130)을 따라 성장한다. 이에 따라, 형성된 판상 산화아연 입자(100)는 평균 입자 크기(S)가 200 내지 1200 nm, 평균 입자 두께(T)는 10 내지 100 nm를 가지며, 평균 입자 두께(T)에 대한 평균 입자 크기(S)의 종횡비는 10:1 내지 50:1을 가지는 육각 판상 형상을 갖는다. Through the discharge of the zinc-air battery system 200, a zinc salt and optionally a salt are added to the electrolyte solution 230 containing an anionic zinc compound and initial zinc oxide molecules, and these reactants react to form zinc oxide crystals. is formed (step S230). The added zinc salt reacts with the anionic zinc compound to grow zinc oxide crystals. As described above, the anionic zinc compound is the non-polar surface of the initial zinc oxide molecules remaining in the electrolyte solution 230.

Due to the distribution along the surface 130, the zinc oxide crystals formed by the reaction of the anionic zinc compound with the added zinc salt are non-polar surfaces.

It grows along face 130. Accordingly, the plate-shaped zinc oxide particles 100 formed have an average particle size (S) of 200 to 1200 nm, an average particle thickness (T) of 10 to 100 nm, and an average particle size relative to the average particle thickness (T) ( S) has a hexagonal plate-like shape with an aspect ratio of 10:1 to 50:1.

On the other hand, when an inorganic acid such as hydrochloric acid, sulfuric acid, or nitric acid is used instead of a zinc salt, a neutralization reaction between the anionic zinc compound and the inorganic acid occurs very rapidly, and zinc oxide particles grow too rapidly. In the case of using such an acid-neutralization method, a phenomenon of aggregation or agglomeration of the grown zinc oxide primary particles 100 occurs. Accordingly, the zinc oxide particles that are actually synthesized have a particle size exceeding the micro size while a large number of particles are agglomerated. It is difficult to expect the intended UV blocking effect from the zinc oxide particles thus prepared.

However, when the zinc salt is used to react with the anionic zinc compound remaining in the electrolyte 230 according to the present invention, the reaction rate between the zinc salt and the anionic zinc compound is controlled while the shape and size distribution of the particles are controlled to form a plate shape. Nano-sized zinc oxide particles 100 having a structure may be manufactured.

As described above, by reacting the primary zinc oxide molecules included in the electrolyte 230 with the anionic zinc compound and zinc salt, the ratio of the particle size distribution d ₉₀ to the average particle size (S) is 1.0 to 3.5, and the average The plate-shaped zinc oxide particles 100 having a ratio of d[ _4,3 ], which is an average diameter calculated from the volume of the zinc oxide particles to the particle size (S), ranges from 0.3 to 2.0. For example, the particle size distribution d ₉₀ of the zinc oxide particles 100 may be 600 to 2000 nm, and d[ _4,3 ] may be 250 to 650 nm.

In one exemplary aspect, the zinc salt may be added at a concentration of approximately 0.1 to 2.0 M, preferably 0.5 to 1.5 M. When the concentration of the zinc salt is less than 0.1 M, the average particle size (S) of the finally produced zinc oxide particles 100 may be excessively small and the light transmittance may decrease. When the concentration of the zinc salt exceeds 2.0 M concentration, the average particle size (S) of the plate-like zinc oxide particles 100 becomes excessively large and/or the primary particles agglomerate with each other, and the size of the plate-like zinc oxide particles 100 becomes unbalanced. can be homogeneous. Accordingly, the light transmittance of the plate-shaped zinc oxide particles 100 may decrease, and the application properties or formulation stability may decrease.

In order to form the plate-like zinc oxide particles 100, a zinc salt that may be added to the electrolyte solution 230 including an anionic zinc compound and primary zinc oxide particles may react with the anionic zinc compound to grow zinc oxide crystals. If there is, it is not particularly limited. For example, the zinc salt may be selected from the group consisting of organic zinc, inorganic zinc, and combinations thereof.

For example, the organic acid zinc may include C ₁ -C ₂₀ organic acid zinc, preferably C ₁ -C ₁₀ organic acid zinc. In one embodiment, the organic zinc acid is zinc monocarboxylic acids such as zinc formate, zinc acetate, zinc lactate, zinc propionate, zinc gluconate, zinc benzoate and combinations thereof and/or zinc oxalate, zinc malonate, zinc tartrate, zinc citrate, succinate. polyhydric carboxylic acids such as zinc and combinations thereof, but are not limited thereto. The inorganic acid zinc may include, but is not limited to, zinc nitrate, zinc sulfate, zinc chloride, and combinations thereof.

면(130)을 따라 존재하는 다수의 음이온 아연 화합물과 반응하면서,

면(130)을 따라 산화아연 결정을 성장시킬 수 있다. For example, when organic acid zinc is used as the zinc salt, organic acid anions dissociated from the zinc salt surround terminal zinc atoms distributed on the polar surface (110) of the zinc oxide crystal (100). On the other hand, the cationic zinc dissociated from the zinc salt is a non-polar surface perpendicular to the [0001] polar surface of the primary zinc oxide molecule in the electrolyte 230.

Reacting with a number of anionic zinc compounds present along side 130,

Zinc oxide crystals may be grown along side 130 .

In an exemplary aspect, in the step of forming zinc oxide crystals (step S230), other salts other than the above-described zinc salt may be further added to the electrolyte 230 including primary zinc oxide molecules and an anionic zinc compound. there is. The added salt is not particularly limited, but may be selected from the group consisting of C _{1 -C 10 organic acid salts of alkali metals, C 1 -C 10 organic acid} salts of alkaline earth metals, and combinations thereof.

In an exemplary aspect, the other salt may be, but is not limited to, an alkali or alkaline earth metal salt of a single carboxylic acid and/or an alkali or alkaline earth metal salt of a polyvalent carboxylic acid, such as those described for organic acids zinc.

Alkali metal (alkaline earth metal) organic acid salts are dissociated into alkali metal (alkaline earth metal) cations and organic acid anions in the electrolyte 230 . At this time, the organic acid anion dissociated from the organic acid salt also surrounds the terminal zinc atoms present on the [0001] face 110 of the zinc oxide crystal, and the shape and/or particle size of the plate-like zinc oxide particles 100 finally produced The uniformity of the distribution can be further improved.

For example, the salt, which may be an alkali metal organic acid salt or an alkaline earth metal organic acid salt, may be added at a concentration of 0.01 to 0.5 mM, preferably 0.05 to 0.2 mM. When the concentration of the salt satisfies the aforementioned range, the finally synthesized zinc oxide particles 100 may have an intended shape (size, thickness, aspect ratio) and/or particle size distribution.

In an optional aspect, a salt such as an alkali metal organic acid salt or an alkaline earth metal organic acid salt may be added to the electrolyte solution 230 prior to optionally adding a zinc salt to the electrolyte solution 230 . When zinc salt is added to the electrolyte solution 230, potassium hydroxide in the electrolyte solution 230 reacts with a zinc salt (for example, organic acid zinc), and organic acid potassium is produced as a by-product. As the pH of the electrolyte solution 230 rapidly fluctuates, growth of the plate-like zinc oxide particles 100 may be delayed or plate-like zinc oxide particles 100 having an insufficient aspect ratio may be synthesized.

In an exemplary aspect, the salt added to the electrolyte solution 230 before adding the zinc salt may be dissolved in water at a concentration of 5 to 40% (w/v). When the salt is added to the electrolyte 230 and then the zinc salt is added to the electrolyte 230, the pH of the electrolyte 230 does not change rapidly even if a by-product is generated by reacting the zinc salt with the potassium hydroxide in the electrolyte 230. .

When a salt is first added to the electrolyte solution 230 and then a zinc salt is added to the electrolyte solution 230 to react with the electrolyte solution 230, the finally synthesized plate-like zinc oxide particles 100 have a particle size of approximately 100 while maintaining the primary particle size. A lattice having a cluster shape of 5 to 15 pieces is formed. Although clusters are formed, d ₉₀ of the plate-shaped zinc oxide particles 100 does not increase, and therefore, excellent light blocking rate, heat blocking rate, and antibacterial and antiviral properties can be obtained.

In one exemplary aspect, adding a zinc salt (optionally including other salts) to the electrolyte solution 230 comprising primary zinc oxide molecules and an anionic zinc compound is performed at a temperature of 60 to 95° C., for example, 70° C. to 90 °C, and then, the reaction related to the growth and aging of zinc oxide crystals according to the reaction of the zinc salt and the anionic zinc compound may be carried out at a temperature of 50 to 95 °C, for example, 60 to 90 °C. there is. In addition, the zinc salt (and optionally other salts) may be added to the electrolyte solution 230 at a rate of about 2.0 to 5 L/minute, for example, 2.5 to 4.5 L/minute, but is not limited thereto.

When the plate-shaped zinc oxide particles 100 having a predetermined shape and particle size distribution are sufficiently grown by adding a zinc salt and, if necessary, a salt, the electrolyte solution 230 containing the plate-shaped zinc oxide particles 100 is filtered and washed ( Step S240). For example, when the synthesis reaction is finished, liquid components are first separated from the electrolyte solution 230 containing the zinc oxide particles 100 using a filter paper of an appropriate size in a Buchner funnel.

At this time, a filter paper of an appropriate size capable of separating the zinc oxide particles 100, which is a product, in the Buchner funnel, for example, 0.1 to 10 μm, preferably 0.2 to 3 μm, may be used. Subsequently, by-products other than zinc oxide particles (eg unreacted anionic zinc compounds, zinc salts and salts, etc.) are washed with a solvent that does not affect the physical properties of zinc oxide particles, such as distilled water, and finally zinc oxide particles Only (100) can be separated (step S240). The washing solvent is not particularly limited, and may be washed one or more times using an excess amount of solvent, for example, 10 to 30 times the volume of water compared to the electrolyte solution 230 .

After the filtering and washing step (Step S240) is completed, the prepared zinc oxide particles 100 are dried by a method such as hot air drying to finally prepare plate-shaped zinc oxide particles 100 (Step S250). In an exemplary aspect, the drying process may be performed until the water content contained in the plate-like zinc oxide particles 100 is less than 5.0%, and when hot air drying is applied, the drying temperature is approximately 150 ° C to 500 ° C, preferably It may be carried out in the range of 150 ° C. to 400 ° C., and may proceed for about 20 hours or more, for example, 24 hours to 48 hours.

If necessary, the surface of the synthesized plate-like zinc oxide particles 100 may be treated with the surface treatment agent described above (step S260). The surface treatment may be performed to have a surface treatment layer with a surface treatment agent in an amount of 0.1 to 20% by weight based on the total weight of the surface-treated plate-like zinc oxide particles 100. If the content of the surface treatment agent is less than 0.1% by weight, it is difficult to improve the dispersion characteristics of the plate-like zinc oxide particles 100 by surface treatment, and if the content of the surface treatment agent exceeds 20% by weight, the physical properties of the plate-like zinc oxide particles 100 There is a risk of deterioration.

[Application of Zinc Oxide Particles]

The present invention also provides a sunscreen agent comprising the plate-shaped zinc oxide particles 100 having the above-described shape and particle size distribution, for example, a sunscreen agent, a heat radiation agent, a cosmetic composition for sunscreen and/or preventing skin aging, an antibacterial agent and/or It's about antivirals.

It is known that when the temperature of the skin exceeds 40° C., thermal aging of the skin proceeds, and when the temperature exceeds 43° C., damage to the skin begins. The plate-shaped zinc oxide particles 100 according to the present invention have improved blocking properties against light rays in a wide wavelength band, and thus have excellent blocking properties against light rays in the visible and infrared regions as well as rays in the ultraviolet region. Therefore, it is also possible to prevent skin aging by preventing an increase in skin temperature due to these rays.

For example, the plate-shaped zinc oxide particles 100 may be used as a functional material for a light blocking agent and/or a heat dissipating agent. Zinc oxide particles manufactured according to a conventional manufacturing method have a spherical shape and have a size of approximately several tens of nanometers. These fine-sized zinc oxide particles may have a UV blocking effect, but due to their small size, they penetrate into the pore cells of the human skin, raising controversy about their harm to the human body.

Since the plate-shaped zinc oxide particles 100 prepared according to the present invention have a particle size (S) of 200 nm or more, they do not penetrate into human skin cells, and thus have a harmless and sufficient light blocking effect and/or heat dissipation effect.

In addition, when conventional zinc oxide particles having a size of hundreds of nanometers are to be applied as sunscreens in sunscreen cosmetics, there is a problem in that a sunscreen phenomenon is lowered due to a cloudiness phenomenon when formulated into cosmetics. However, in the planar zinc oxide particles 100 prepared according to the present invention, the aspect ratio of the average particle size (S) to the average particle thickness (T) is very large, and there is no aggregation of primary particles. Therefore, despite the size of hundreds of nanometers or more, it is possible to prevent cloudiness during the formulation process, so that the light blocking effect is not deteriorated and the stability of the formulation is excellent. As such, the plate-shaped zinc oxide particles 100 manufactured according to the present invention solve the problem of harmfulness to the human body and at the same time realize efficient light blocking effect, heat blocking effect, and skin aging prevention effect.

In an exemplary aspect, the light blocking agent and/or the heat dissipating agent may include inorganic particles different from the above-described planar zinc oxide particles 100 having a unique particle structure, particle size, particle shape, and particle size distribution.

Other inorganic particles that may be added to the sunscreen and/or heat-dissipating agent and the cosmetic composition containing the same include inorganic metal oxide particles such as titanium oxide particles, zinc oxide particles, and aluminum oxide particles, as well as aluminum nitride, boron nitride, carbide, and the like. It may include silicon, silicon nitride, titanium nitride, metal silicon, etc., but is not limited thereto.

For example, the sunscreen and/or heat release agent and other inorganic particles that may be added to the cosmetic composition may include other inorganic particles consisting of titanium oxide particles, zinc oxide particles, and combinations thereof. When the sunscreen, heat-dissipating agent and cosmetic composition contain other inorganic particles in addition to the zinc oxide particles 100 according to the present invention, the weight ratio of the zinc oxide particles 100 and the other inorganic particles is 1:10 to 10:1. , For example, it may be formulated in a weight ratio of 1:5 to 5:1, but is not limited thereto. The size of other inorganic particles that can be applied as a light blocking material or a heat dissipating material is not particularly limited, and inorganic particles having an average particle size of 10 to 100 nm and/or inorganic particles having an average particle size of 200 to 1000 nm are not particularly limited. can include

For example, the plate-like zinc oxide particles 100 (optionally other inorganic particles) may be included in an amount of 3 to 20% by weight, for example, 4 to 15% by weight in the light blocking agent, heat radiation agent and cosmetic composition. Not limited. If the content of the light blocking material or heat blocking agent including the plate-shaped zinc oxide particles 100 and other inorganic particles in the light blocking agent, heat dissipating agent, and cosmetic composition is less than 3% by weight, it is difficult to expect light blocking and heat blocking effects, and 20 weight If % is exceeded, dispersion characteristics and stability of the formulation may deteriorate or these light blocking materials or heat dissipating materials may aggregate.

If necessary, the light blocking agent and/or the heat dissipating agent may further include a binder and a diluent for dispersing the zinc oxide particles 100 and the inorganic particles. The binder may be a thermoplastic or thermosetting resin. For example, the binder is an epoxy resin, phenol resin, polyphenylene sulfide (PPS) resin, polyester resin, polyamide, polyimide, polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, fluorine resin , polymethyl methacrylate, ethylene/ethyl acrylate copolymer (EEA) resin, polycarbonate, polyurethane, polyacetal, polyphenylene ether, polyetherimide, acrylonitrile-butadiene-styrene copolymer (ABS) resin, It may include, but is not limited to, liquid crystal resins (LCP), silicone resins, acrylic resins, and combinations thereof.

For example, the light blocking agent and/or the heat dissipating agent is obtained by kneading a thermosetting resin binder, plate-like zinc oxide particles 100, and optionally inorganic particles in a molten state, or a thermosetting resin binder and phanate zinc oxide particles ( 100) and optional inorganic particles, followed by heating and hardening, or may be obtained by dispersing zinc oxide particles 100 and optionally inorganic particles in a resin solution or dispersion.

As will be described later, the plate-like zinc oxide particles 100 according to the present invention or a sunscreen containing the same can be used as a cosmetic product for sunscreen (for example, sunscreen) and/or for preventing skin aging. For example, for formulation into cosmetics, the surface of the plate-shaped zinc oxide particles 100 may be hydrophobized. The hydrophobic treatment is performed by a known method without any particular limitation. For example, treatment using silicones such as methylhydrogenpolysiloxane, methylhydrogenpolysiloxane-dimethylpolysiloxane copolymer, and methylpolysiloxane; treatment using silane compounds such as octyltriethoxysilane and hexyltrimethoxysilane; treatment with fatty acids such as palmitic acid and stearic acid; metal soap treatment using alkali metal salts or alkaline earth metal salts of the fatty acids; and fluorine treatment using perfluoroalkyl phosphate diethanol amine salt, perfluoroalkyl trimethoxysilane, and the like.

As the binder included in the light blocking agent and/or the heat dissipating agent, for example, an aqueous acrylic binder may be used. The aqueous acrylic binder may be (co)polymerized with a monomer mainly composed of (meth)acrylic acid derivatives such as acrylic acid and methacrylic acid derivatives. In this specification, unless otherwise stated, the term '(meth)acrylic acid' refers to acrylic acid and methacrylic acid, and '(meth)acrylate' refers to methacrylate and acrylate.

According to an exemplary aspect, the aqueous acrylic binder is (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate Lauryl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxymethyl ( Meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate, acetoneacrylamide. It is a polymer of (meth)acrylate-based monomers selected from the group consisting of cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and combinations thereof. If the content of the binder is 5% by weight, there is a problem in mixing and transparency when making a cosmetic formulation, for example, and if it exceeds 30% by weight, there is a concern that the sunscreen effect may be lowered.

The diluent is added to adjust the viscosity of the light blocking agent and/or heat dissipating agent, and is not particularly limited as long as it meets the purpose of the present invention. For example, at least one selected from secondary distilled water, tertiary distilled water, isopropylalcohol, EC (Ethyl Cellosolve), ethanol, or MEK may be used.

As described above, the plate-shaped zinc oxide particles 100 are excellent in light blocking effect and heat blocking effect. Therefore, the plate-shaped zinc oxide particles 100 may be used alone or in combination with other inorganic particles as a functional material for cosmetics for blocking sunlight and/or preventing skin aging. For example, the light blocking material or heat dissipating material including the plate-shaped zinc oxide particles 100 and other inorganic particles of the present invention may be added in a cosmetic composition at a ratio of 5 to 20% by weight, but is not limited thereto.

The cosmetic composition according to the present invention may further include additives commonly used in the field, such as polyols, emulsifiers, and surfactants, in addition to the light blocking material including the plate-shaped zinc oxide particles 100.

For example, the cosmetic composition comprising the plate-shaped zinc oxide particles 100 may include surfactants, emulsifiers, soap acids, solvents, binders, diluents, lubricants, stabilizers, fragrances, water, lower alcohols, thickeners, chelating agents, pigments, Preservatives, colorants, preservatives, antibiotics, antioxidants, antifoaming agents, antibacterial agents, antiredeposition agents, enzymes, vegetable or mineral oils, oils such as fats, fluorescent substances, fungicides, hydrotropes, humectants, fragrances, fragrance carriers, preservatives, It may contain one or more cosmetically acceptable excipients selected from the group consisting of proteins, silicones, solubilizers, sugar derivatives, sunscreens, vitamins, plant extracts, and waxes.

The cosmetic composition according to the present invention may be prepared in any formulation commonly prepared in the art, for example, a solution, suspension, emulsion, paste, gel, cream, lotion, powder, It may be formulated as an oil, powder foundation, emulsion foundation, wax foundation and spray, but is not limited thereto.

For example, the cosmetics of the present invention may have any form such as oil-based cosmetics, water-based cosmetics, O/W type cosmetics, and W/O cosmetics. More specifically, the cosmetic of the present invention may be formulated into a sunscreen, softening lotion, astringent lotion, nourishing lotion, nourishing cream, massage cream, essence, eye cream, pack, spray, sunscreen agent or powder formulation.

In an exemplary aspect, when the formulation of the cosmetic according to the present invention is a paste, cream or gel, animal oil, vegetable oil, wax, paraffin, starch, tracanth, cellulose derivative, polyethylene glycol, silicone, bentonite, silica, Talc or zinc oxide or the like may be used. In addition, when the cosmetic formulation according to the present invention is a powder or spray, lactose, talc, silica, aluminum hydroxide, calcium silicate or polyamide powder may be used as a carrier component, and in particular, in the case of a spray, chlorofluoro They may contain propellants such as hydrocarbons, propane/butane or dimethyl ether.

In addition, when the formulation of the cosmetic according to the present invention is a solution or emulsion, a solvent, solubilizing agent or emulsifying agent is used as a carrier component, for example, water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate , propylene glycol, 1,3-butyl glycol oil, glycerol aliphatic esters, polyethylene glycol or fatty acid esters of sorbitan. On the other hand, when the formulation of the cosmetic according to the present invention is a suspension, water (for example, ion-exchanged water or purified water) as a carrier component, a liquid diluent such as ethanol or propylene glycol, ethoxylated isostearyl alcohol, polyoxyethylene sorbitol Suspending agents such as esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminum meta hydroxide, bentonite, agar or tracanth and the like may be used.

For example, the cosmetic of the present invention may use any water-based component or oil-based component that can be used in the field of cosmetics in addition to the light blocking material including the plate-shaped zinc oxide particles 100.

The aqueous component and the oil component are not particularly limited, and examples include oil, surfactants, moisturizers, higher alcohols, sequestering agents, natural and synthetic polymers, water-soluble and oil-soluble polymers, UV shielding agents, various extracts, Inorganic and organic pigments, inorganic and organic clay minerals, inorganic and organic pigments treated with metal soap or silicon, colorants such as organic dyes, preservatives, antioxidants, pigments, thickeners, pH adjusters, fragrances, cooling agents ), an antiperspirant, a bactericide, and a skin activator may be contained.

Specifically, one or two or more of the ingredients listed below can be arbitrarily blended to produce the desired cosmetic product by a conventional method. The compounding amount of these compounding components is not particularly limited as long as it does not impair the effects of the present invention.

The oil component is not particularly limited, and for example, avocado oil, camellia oil, tortoise oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, sesame oil, almond oil (杏仁油), wheat germ oil, sasanqua oil, castor oil, linseed oil, surflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, sesame oil, milkshake, rice bran oil, Chinese tung oil oil), Japanese tung oil, jojoba oil, germ oil, triglycerol, glycerin trioctanoate, glycerin triisopalmitate, cacao butter, coconut oil, hemp oil, hydrogenated palm oil, palm oil, Beef tallow, lamb tallow, hardened beef tallow, palm kernel oil, pork tallow, beef bone tallow, wax kernel oil, hardened oil, beef tallow wax), Japan wax, hydrogenated castor oil, beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, insect wax, spermaceti wax, Montane wax, steel wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether , POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, liquid paraffin, ozokerite, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax and the like.

The lipophilic nonionic surfactant is not particularly limited, and examples thereof include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan sesqui. Sorbitan fatty acid esters such as oleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, and diglycerol sorbitan tetra-2-ethylhexylate, mono-cottonseed oil fatty acid glycerin, mono-erucic acid glycerin, cess Glycerol polyglycerin fatty acids such as glycerin trioleate, glycerin monostearate, α,α'-glycerin oleate pyroglutamate, glycerin monostearate malic acid, propylene glycol fatty acid esters such as propylene glycol monostearate, hydrogenated castor oil derivatives, Glycerin alkyl ether etc. are mentioned.

The hydrophilic nonionic surfactant is not particularly limited, and examples thereof include POE sorbitan fatty acid esters such as POE sorbitan monostearate, POE sorbitan monooleate, POE sorbitan tetraoleate, POE sorbitan monolaurate, POE sorbitol fatty acid esters such as POE sorbitol monooleate, POE sorbitol pentaoleate, POE sorbitol monostearate, etc., POE glycerin monostearate, POE glycerin monoisostearate, POE glycerin triisostearate, etc. POE fatty acid esters such as POE glycerin fatty acid esters, POE monooleate, POE distearate, POE monodioleate, ethylene glycol distearate, POE lauryl ether, POE oleyl ether, POE stearyl ether, POE beta POE alkyl ethers such as henyl ether, POE 2-octyldodecyl ether, and POE cholestanol ether, POE alkylphenyl ethers such as POE octylphenyl ether, POE nonylphenyl ether, POE dinonylphenyl ether, pluronic, etc. POE/POP alkyl ethers such as fluaronic type, POE/POP cetyl ether, POE/POP 2decyltetradecyl ether, POE/POP monobutyl ether, POE/POP hydrogenated lanolin, POE/POP glycerin ether, etc. , tetra POE/tetra POP ethylenediamine condensates such as Tetronic, POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, POE hydrogenated castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid mono POE castor oil hydrogenated castor oil derivatives such as isostearic acid diester, POE hydrogenated castor oil maleic acid, POE beeswax/lanolin derivatives such as POE sorbit beeswax, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc. of alkanolamide, POE propylene glycol fatty acid ester, POE alkylamine, POE fatty acid amide, sucrose fatty acid ester, POE nonylphenylformaldehyde condensate, alkylethoxydimethylamine oxide, trioleyl phosphoric acid, etc. can be heard

Examples of other surfactants include fatty acid soaps, higher alkyl sulfate ester salts, POE triethanolamine lauryl sulfate, and anionic surfactants such as alkyl ether sulfate ester salts, alkyltrimethylammonium salts, alkylpyridinium salts, alkyl quaternary ammonium salts, and alkyl Cationic surfactants such as dimethylbenzylammonium salts, POE alkylamines, alkylamine salts, and polyamine fatty acid derivatives, and amphoteric surfactants such as imidazoline-based amphoteric surfactants and betaine-based surfactants are used within a range without problems in stability and skin irritation. may be combined.

The moisturizing agent is not particularly limited, and examples thereof include xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, and lactic acid. sodium, bile salts, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Rosa roxburghii extract, yarrow extract, melilot extract, and the like. there is.

The higher alcohol is not particularly limited, and examples thereof include straight-chain alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol; monostearyl glycerin ether ( branched chain alcohols such as batyl alcohol), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, and octyldodecanol.

The sequestering agent is not particularly limited, and examples thereof include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, and the like.

The natural water-soluble polymer is not particularly limited, and examples thereof include gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, queen's seed (quince), algae (algae) colloid (brown algae extract), starch (rice, corn, potato, wheat), vegetable polymers such as glycyrrhizic acid, microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, collagen, casein, albumin , and animal-based polymers such as gelatin.

The semi-synthetic water-soluble polymer is not particularly limited, and examples thereof include starch-based polymers such as carboxymethyl starch and methylhydroxypropyl starch, methylcellulose, nitrocellulose, ethylcellulose, methylhydroxypropylcellulose, and hydroxyethyl. and cellulose-based polymers such as cellulose, cellulose sodium sulfate, hydroxypropyl cellulose, carboxymethylcellulose sodium (CMC), crystalline cellulose and cellulose powder, and alginic acid-based polymers such as sodium alginate and propylene glycol alginate.

The synthetic water-soluble polymer is not particularly limited, and examples thereof include vinyl-based polymers such as polyvinyl alcohol, polyvinylmethyl ether, and polyvinylpyrrolidone, polyoxyethylene-based polymers such as polyethylene glycol 20,000, 40,000, and 60,000, and polyoxyethylene glycol. Ethylene polyoxypropylene copolymer copolymer polymers, acrylic polymers such as sodium polyacrylate, polyethyl acrylate and polyacrylamide, polyethyleneimine, and cationic polymers.

The inorganic water-soluble polymer is not particularly limited, and examples thereof include bentonite, silicic acid AlMg (veegum), laponite, hectorite, and silicic anhydride.

Other UV-blocking agents are not particularly limited, and examples thereof include para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N , Benzoic acid-based UV shielding agents such as N-dimethyl PABA ethyl ester and N,N-dimethyl PABA butyl ester; anthranilic acid-based UV shielding agents such as homomenthyl-N-acetylantranilate; salicylic acid-based UV shielding agents such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanolphenyl salicylate; Octylcinnamate, Ethyl-4-isopropylcinnamate, Methyl-2,5-diisopropylcinnamate, Ethyl-2,4-diisopropylcinnamate, Methyl-2,4-diisopropylcinnamate, Propyl -p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate , cinnamic acid-based ultraviolet rays such as ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, and glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate masking agent; 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzo Phenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy- benzophenone-based ultraviolet ray shielding agents such as 3-carboxybenzophenone; 3-(4'-methylbenzylidene)-d,l-camphor, 3-benzylidene-d,l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2 '-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenylbenzotriazole, Dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5-(3,3-dimethyl-2-norbornylidene)-3-pentan-2-one, etc. It can also be used in combination with an inorganic UV-blocking agent such as titanium oxide particles or zinc oxide particles not applicable to the present invention.

Other pharmaceutical ingredients are not particularly limited, and examples include vitamin A oil, retinol, retinol palmitate, innocitrate, pyridoxine hydrochloride, benzyl nicotinate, nicotinic acid amide, DL-α-tocopherol nicotinate, magnesium ascorbic acid phosphate, 2- vitamins such as O-α-D-glucopyranosyl-L-ascorbic acid, vitamin D2 (ergocalciferol), dl-α-tocopherol, dl-α-tocopherol acetate, pantothenic acid, and biotin; hormones such as estradiol and ethinylestradiol; amino acids such as arginine, aspartic acid, cystine, cysteine, methionine, serine, leucine, and tryptophan; anti-inflammatory agents such as allantoin and azulene, whitening agents such as arbutin; astringents such as tannic acid; Refreshing agents, such as L-menthol and camphor, sulfur, lysozyme chloride, and pyridoxine chloride are mentioned.

The various extracts are not particularly limited, and examples include Houttuynia cordata extract, Phellodendron bark extract, melilot extract, dead nettle extract, licorice extract, and peony root. ) extract, soapwort extract, luffa extract, cinchona extract, strawberry geranium extract, sophora root extract, nuphar extract, fennel extract, primrose extract, rose extract, Rehmannia Root extract, lemon extract, lithospermum extract, aloe extract, calamus root extract, eucalyptus extract, field horsetail extract, sage extract, thyme extract, tea extract, seaweed extract, cucumber extract, cloves Clove Extract, Raspberry Extract, Melissa Extract, Carrot Extract, Horse Chestnut Extract, Peach Extract, Maple Leaf Extract, Mulberry Extract, Knapweed Extract, Hamamelis Extract, Placenta Extract, A thymus extract, a silk extract, licorice extract, etc. are mentioned.

In addition, the plate-like zinc oxide particles 100 have minimized surface defects and can be used as an active ingredient of an antibacterial composition, an antiviral composition, or an antibacterial agent and/or an antiviral agent. Hereinafter, it should be noted that antimicrobial compositions, antiviral compositions, antibacterial agents, and antiviral agents are collectively referred to as 'antibacterial compositions, etc.'.

As described above, the aspect ratio of the plate-shaped zinc oxide particles 100 is very large, and the specific surface area of the polar face is very large. When a matrix coated with an antibacterial composition containing plate-like zinc oxide particles comes into contact with moisture in the air, the zinc metal component of zinc oxide present on the surface of the matrix is ionized and eluted, and the ionized zinc metal component destroys the bacterial cell wall. It is adsorbed to constituting negatively charged components (for example, teichoic acid present in the cell wall of Gram-positive bacteria or a supporting polysaccharide present in the outer membrane of Gram-negative bacteria).

The ionized zinc metal component is adsorbed on the surface of harmful organisms such as bacteria and viruses, and the concentration of ionized zinc metal ions adsorbed on the surface of harmful organisms is locally increased, suppressing the metabolism of harmful organisms and reducing the risk of harmful organisms. death can be induced.

The plate-shaped zinc oxide particles 100 have a large specific surface area on the polar surface. When the plate-like zinc oxide particles 100 come into contact with air or moisture in the air, by the electrostatic attraction generated by the negative ions or cations present on the wide polar surface of the plate-like zinc oxide particles 100, the plate-like zinc oxide particles 100 ), and the air or moisture in contact with it is converted into active ions. The converted active ions can kill bacteria while being adsorbed on the bacterial cell wall. In addition, the converted active ion can pass through the cell membrane of the virus after being adsorbed on the surface of the virus, thereby weakening the activity of the virus.

Accordingly, the plate-shaped zinc oxide particles 100 have antiviral and antibacterial properties. For example, the plate-like zinc oxide particles 100 exhibit antibacterial and antiviral activity against not only gram-positive and gram-negative bacteria, but also coronavirus.

In an exemplary aspect, the antibacterial composition and the like may include other inorganic particles in addition to the plate-like zinc oxide particles 100 . Other usable inorganic particles may include aluminum nitride, boron nitride, silicon carbide, silicon nitride, titanium nitride, metal silicon, as well as inorganic metal oxide particles such as titanium oxide particles, zinc oxide particles, and aluminum oxide particles. . For example, other inorganic particles that may be added to the antimicrobial composition or the like may include inorganic metal oxide particles such as zinc oxide particles, titanium oxide particles, aluminum oxide particles. For example, in the antimicrobial composition, etc., the planar zinc oxide particles 100 and other inorganic particles are blended in a weight ratio of 1:9 to 9:1, for example, 8:2 to 2:8, optionally 5:5. It may be, but is not limited thereto.

In an exemplary aspect, the planar zinc oxide particles 100 and optionally added other inorganic particles in the antimicrobial composition may be included in an amount of 3 to 20% by weight, for example, 5 to 20% by weight. The antibacterial composition and the like may be formulated in the form of a cream or coated on a base film in the form of a thin film.

In an exemplary aspect, the antimicrobial composition and the like may include a binder. The binder fixes the plate-shaped zinc oxide particles 100, which is an active ingredient of an antibacterial composition or the like. Binders may include thermosetting resins, UV curable resins, simultaneous heat and UV curable resins, moisture curable resins, and combinations thereof. For example, binders may include polyurethane, polyurea, acrylic resin, epoxy resin, polypropylene, polyethylene, polysulfone, polystyrene, polyvinylchloride, polyethylene terephthalate, polyester, nylon, silicone resin, and combinations thereof. may, but is not limited thereto.

In an exemplary aspect, the binder may be used in an amount of 80 to 99% by weight, for example, 80 to 95% by weight of the antimicrobial composition or the like. If the content of the binder included in the antibacterial composition or the like is less than 90% by weight, the curing speed may be slowed and the adhesion to the adhered surface may be reduced. If the content of the binder included in the antibacterial composition or the like exceeds 99% by weight, the content of the plate-shaped zinc oxide particles 100, which is an active ingredient, may decrease, and thus antibacterial and/or antiviral properties may deteriorate.

Optionally, the antimicrobial composition and the like may further contain dispersants, antifoaming agents and other functional additives. The dispersant uniformly disperses the binder and the plate-shaped zinc oxide particles 100 included in the antibacterial composition or the like. In one aspect, the dispersant may use water and/or an organic solvent. For example, the dispersant is water, alcohol, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (methyl cellusolve, ethyl cellusolve, butyl cellosolve, etc.), esters (ethyl cellusolve, etc.) acetate, butyl acetate, etc.), dimethylformamide, n-methylpyrrolidine, propylene glycol monomethyl ether acetate, dibasic ester, dimethyl carbonate, toluene, and combinations thereof, but is not limited thereto. .

Optionally, the dispersant may be an organic dispersant selected from the group consisting of polyhydroxy stearic acid, castor oil phosphate, polyglycerol esters, polyacrylic acid, polyacrylic acid salts, and combinations thereof. In another aspect, the dispersant may be an inorganic dispersant such as a magnesium-based dispersant. For example, the organic dispersant and/or the inorganic dispersant may be added in an amount of about 0.1 to 5% by weight, for example, 0.5 to 2% by weight in the antimicrobial composition.

The dispersant may be included in an amount of 10 to 900 parts by weight based on 100 parts by weight of the mixture of the binder and the plate-like zinc oxide particles 100 constituting the antimicrobial composition. If the content of the dispersant included in the antimicrobial composition or the like is less than 10 parts by weight based on 100 parts by weight of the mixture of the binder and the plate-like zinc oxide particles 100, the binder and the plate-like zinc oxide are applied to the object or film to be coated or the film is manufactured. Difficulties may arise in uniformly dispersing the particles 100 . In particular, if the content of the dispersant is less than 100 parts by weight based on 100 parts by weight of the mixture of the binder and the plate-shaped zinc oxide particles 100, the viscosity of the antimicrobial composition may increase, making it difficult to use it as a spray.

On the other hand, if the content of the dispersant exceeds 900 parts by weight based on 100 parts by weight of the mixture of the binder and the plate-shaped zinc oxide particles 100, the other components can be smoothly dispersed, but the antibacterial composition or the like may flow down along the coated surface. can

The antifoaming agent is added when the antimicrobial composition or the like is used as a spray composition, and provides a function of removing air bubbles generated on the surface of the coated object when the antibacterial composition or the like is applied to the object (mother body) in a spray method. In particular, the antifoaming agent can prevent the coated surface from being bent and deformed due to the generation of bubbles.

In the antimicrobial composition or the like, the antifoaming agent may be included in an amount of 2 to 3 parts by weight based on 100 parts by weight of the mixture of the binder and the planar zinc oxide particles 100. If the content of the antifoaming agent added to 100 parts by weight of the mixture of the binder and the plate-shaped zinc oxide particles 100 is less than 2 parts by weight, the content of the antifoaming agent included in the antimicrobial composition is low, preventing the generation of bubbles when the antimicrobial composition or the like is applied to the surface of an object. A problem in which the coated surface is deformed in a curved manner may occur because it is not suppressed. If the amount of the antifoaming agent added to 100 parts by weight of the mixture of the binder and the plate-like zinc oxide particles 100 exceeds 3 parts by weight, no additional effect other than the removal of air bubbles may occur and manufacturing cost may increase.

Additives that may be added to the antimicrobial composition and the like may include a silane coupling agent to promote adhesion to the film. At this time, the same silane coupling agent as the surface treatment agent that can be used to treat the surface of the plate-like zinc oxide particles 100 can be used. The silane coupling agent may be added to the antibacterial composition or the like in a ratio of 0.1 to 20 parts by weight based on 100 parts by weight of the mixture of the binder and the plate-like zinc oxysulfate particles 100.

Other additives that can be added to the antibacterial composition or the like may include an antistatic agent to prevent adsorption of dust by reducing the electrical resistance of the film surface to prevent generation of static electricity. The antistatic agent is included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the mixture of the binder and the planar zinc oxide particles 100. If the content of the antistatic agent added to 100 parts by weight of the mixture of the binder and the plate-shaped zinc oxide particles (100) is less than 1 part by weight, the antistatic effect cannot be achieved during film production, and if the content of the antistatic agent exceeds 5 parts by weight, the amount of the antistatic agent increases. The improvement of the effect according to this is insignificant, but the production cost is increased.

In addition, the additive may include a fragrance capable of exhibiting a deodorizing effect and a deodorizing effect by suppressing odor-causing bacteria by an antibacterial component. As the fragrance, it is preferable to use a fragrance with excellent residual fragrance so that an excellent deodorizing effect can be achieved by masking the odor. The spice may be included in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of the mixture of the binder and the planar zinc oxide particles 100.

Optionally, the antimicrobial composition and the like may be applied to a polymer film. For example, the antimicrobial composition may be applied to the surface of a polymer film made in the form of a film to a thickness of 0.01 to 100 μm and used as an antibacterial agent formulated in the form of an antibacterial and/or antiviral film.

For example, the polymer film is polyethylene, polypropylene, expanded polypropylene (EPP), ABS resin, polyethylene terephthalate, polybutylene terephthalate, polybutyrate adipate terephthalate, polyurethane, polystyrene, polyvinyl chloride, polyvinyl Butyral, polyvinyl alcohol, ethylene vinyl acetate, polycarbonate, polylactic acid, polyglycolic acid, polycaprolactone, polylactic acid-polyglycolic acid copolymer, polylactic acid-polycaprolactone copolymer, polyacid anhydride, polybutylene succinates, polyhydroxybutyrates, polyamides, polyacrylates, polymethacrylates, nylons, copolymers thereof, and combinations thereof.

로 열처리하는 단계를 통해 제조될 수 있으나, 이에 한정되지 않는다. For example, the functional film is applied by applying an antibacterial composition or the like to the surface of the polymer film, and providing an amount of ultraviolet (UV) light of 300 to 500 mJ / cm 2 to the polymer film and / or 70 to 80

It may be manufactured through a heat treatment step, but is not limited thereto.

In another exemplary aspect, the antibacterial agent and/or antiviral agent may be prepared in a master batch type. For example, a pellet-type binder, plate-like zinc oxide particles 100 (optionally other inorganic particles), and optionally a magnesium-based dispersant are added to a continuous mixer, and after kneading and dispersion are completed at about 150 to 250 ° C., After extruding and cooling the composite with an extruder, a pelletized master batch can be prepared with a pelletizer.

In another exemplary aspect, it is possible to prepare an injection-type antibacterial agent or the like by mixing the plate-like zinc oxide particles 100 (optionally a mixture of other inorganic particles) with a binder without preparing a masterbatch. In this case, the binder and the plate-like zinc oxide particles 100 (optionally other inorganic particles) are physically pre-mixed, the mixture is put into a kneader and injected, and the binder and the plate-like zinc oxide particles 100 (optionally other inorganic particles) are injected. other inorganic particles) can be sufficiently mixed and dispersed in an antibacterial agent or the like.

Hereinafter, the present invention will be described through exemplary embodiments, but the present invention is not limited to the technical idea described in the following examples.

Synthesis Example 1 Synthesis of Platelet Zinc Oxide Particles

In a zinc-air battery system using zinc metal as the negative electrode and an air electrode using a manganese dioxide catalyst as the positive electrode, sufficient power is generated and the electrolyte solution is recovered while circulating a 45% (w/v) KOH aqueous electrolyte solution for 2-10 hours. did The zinc-air battery was manufactured as follows. First, in order to prepare the cathode, an air anode (10 X 10 cm) composed of cobalt catalyst, Teflon, and carbon powder was prepared. Nickel foam (1 X 1 cm) and wires were connected by lead welding, and a conductive adhesive mixed with epoxy adhesive and nano silver powder was used to bond the nickel foam to which the wires were connected and the air anode. The air anode connected to the electric wire was attached to a plastic special container for experiments with epoxy adhesive. An anode was prepared by attaching an anode active material of metal zinc-aluminum (90-99: 1-10 by weight) electrodeposited with alkali or acid to a cathode current collector having a brass mesh (10 X 10 cm) structure. 450 ml (660 g) of a 45% potassium hydroxide (KOH) solution, which is an electrolyte, was placed in a special container for experiments with an air anode connected to the wire, and a metal cathode was inserted into the electrolyte so as to be submerged.

The recovered electrolyte solution was diluted with a low-concentration KOH aqueous electrolyte solution, and finally zinc acetate and sodium citrate were added to the electrolyte solution containing 8% (w/v) concentration KOH electrolyte and zinc hydroxide at 1M and 0.15 mM concentration, respectively, from 3 to 3.5 mM. It was added at a mixing rate of L/miniute, and a salt neutralization reaction was performed at 80 to 85° C. to precipitate zinc oxide crystals. The solution containing the zinc oxide crystals was filtered to separate from the potassium acetate solution, thoroughly washed with water, and then dried at 120° C. to obtain plate-like zinc oxide ceramic powder.

Synthesis Example 2: Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution was diluted with a low-concentration KOH aqueous electrolyte solution, and finally, the procedure of Synthesis Example 1 was repeated except that zinc acetate and sodium citrate were added to the electrolyte solution containing KOH electrolyte at a concentration of 6.5% (w / v). A plate-shaped zinc oxide ceramic powder was obtained.

Synthesis Example 3 Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution was diluted with a low-concentration KOH aqueous electrolyte solution, and finally, the procedure of Synthesis Example 1 was repeated except that zinc acetate and sodium citrate were added to the electrolyte solution containing KOH electrolyte at a concentration of 6.0% (w / v). A plate-shaped zinc oxide ceramic powder was obtained.

Synthesis Example 4: Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution was diluted with a low-concentration KOH aqueous electrolyte solution, and finally, the procedure of Synthesis Example 1 was repeated except that zinc acetate and sodium citrate were added to the electrolyte solution containing KOH electrolyte at a concentration of 6.0% (w / v). A plate-shaped zinc oxide ceramic powder was obtained.

Synthesis Example 5: Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution was diluted with a low-concentration KOH aqueous electrolyte solution, and finally, the procedure of Synthesis Example 1 was repeated except that zinc acetate and sodium citrate were added to the electrolyte solution containing KOH electrolyte at a concentration of 5.5% (w / v). A plate-shaped zinc oxide ceramic powder was obtained.

Synthesis Example 6: Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution was diluted with a low-concentration KOH aqueous electrolyte solution, and finally, the procedure of Synthesis Example 1 was repeated except that zinc acetate and sodium citrate were added to the electrolyte solution containing 5.0% (w / v) concentration KOH electrolyte. A plate-shaped zinc oxide ceramic powder was obtained.

Synthesis Example 7: Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution was diluted with a low-concentration KOH aqueous electrolyte solution, and finally, the procedure of Synthesis Example 1 was repeated except that zinc acetate and sodium citrate were added to the electrolyte solution containing KOH electrolyte at a concentration of 4.5% (w / v). A plate-shaped zinc oxide ceramic powder was obtained.

Synthesis Example 8: Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution is diluted with a low-concentration KOH aqueous electrolyte solution, and zinc acetate and sodium citrate are finally added to the electrolyte solution containing a 5.0% (w/v) KOH electrolyte at a mixing rate of 3.5 to 4.0 L/minute, Except for the salt neutralization reaction at 90 ° C., the procedure of Synthesis Example 1 was repeated to obtain planar zinc oxide ceramic powder.

Synthesis Example 9 Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution was diluted with a low-concentration KOH aqueous electrolyte solution, and zinc acetate and sodium citrate were finally added to the electrolyte solution containing 5.0% (w/v) KOH electrolyte at a mixing rate of 3.5 to 4.0 L/minute. Except, the procedure of Synthesis Example 1 was repeated to obtain plate-like zinc oxide ceramic powder.

Synthesis Example 10: Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution is diluted with a low-concentration KOH electrolyte solution, and zinc acetate and sodium citrate are finally added to the electrolyte solution containing a 4.5% (w/v) KOH electrolyte at a mixing rate of 3.5 to 4.0 L/minute, Except for the salt neutralization reaction at 90 ° C., the procedure of Synthesis Example 1 was repeated to obtain planar zinc oxide ceramic powder.

Synthesis Example 11: Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution is diluted with a low-concentration KOH aqueous electrolyte solution, and zinc acetate and sodium citrate are finally added to the electrolyte solution containing a 7.5% (w/v) KOH electrolyte at a mixing rate of 3.5 to 4.0 L/minute, Except for the salt neutralization reaction at 90 ° C., the procedure of Synthesis Example 1 was repeated to obtain planar zinc oxide ceramic powder.

Synthesis Example 12 Synthesis of Platelet Zinc Oxide Particles

The surface of the planar zinc oxide ceramic powder synthesized in Synthesis Example 8 was subjected to surface treatment using a silane coupling agent to obtain planar zinc oxide ceramic powder coated with the silane coupling agent. Specifically, the same weight of water as the synthesized zinc oxide particles was mixed, and 95% ethanol in an amount of about 1/2 of the total weight of the zinc oxide particles and water was added and stirred. The silane coupling agent OFS-6341 (Dow Coating) and the diluent OFS-6020 were added in a ratio of 5:1 to the stirred reaction mass, and heated at 60° C. at 400 rpm or more for 2 hours.

Synthesis Example 13 Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution is diluted with a low-concentration KOH aqueous electrolyte solution, and finally 5% (w/v) potassium acetate is added to the electrolyte solution containing 5.0% (w/v) KOH electrolyte in advance to adjust the pH of the reaction solution. Except for adjusting, the procedure of Synthesis Example 8 was repeated to obtain plate-shaped zinc oxide ceramic powder.

Synthesis Example 14: Synthesis of Platelet Zinc Oxide Particles

The recovered electrolyte solution is diluted with a low-concentration KOH aqueous electrolyte solution, and finally 40% (w/v) potassium acetate is added to the electrolyte solution containing 5.0% (w/v) KOH electrolyte in advance to adjust the pH of the reaction solution. Except for adjusting, the procedure of Synthesis Example 8 was repeated to obtain plate-shaped zinc oxide ceramic powder.

Comparative Synthesis Example 1: Synthesis of Zinc Oxide Particles

Zinc oxide ceramic powder was obtained by repeating the procedure of Synthesis Example 1, except that 17.5% (w/v) aqueous hydrochloric acid was added to the recovered aqueous electrolyte solution to adjust the pH to 7-8 to neutralize it.

Comparative Synthesis Example 2: Synthesis of Zinc Oxide Particles

Zinc oxide ceramic powder was obtained by repeating the procedure of Synthesis Example 1 except that the recovered aqueous electrolyte solution was neutralized by adding 15.0 (w/v) hydrochloric acid aqueous solution.

Comparative Synthesis Example 3: Synthesis of Zinc Oxide Particles

Zinc oxide ceramic powder was obtained by repeating the procedure of Synthesis Example 1 except that the recovered aqueous electrolyte solution was neutralized by adding 12.5 (w/v) hydrochloric acid aqueous solution.

Comparative Synthesis Example 4: Synthesis of Zinc Oxide Particles

Zinc oxide ceramic powder was obtained by repeating the procedure of Synthesis Example 1 except that sodium citrate and zinc acetate were added to the recovered aqueous electrolyte solution and neutralized by adding 17.5 (w/v) hydrochloric acid aqueous solution.

Example 1: Analysis of shape, crystallographic structure and particle size distribution of inorganic particles

Synthesis Examples 1 to 14, Comparative Synthesis Examples 1 to 4 (Comparative Examples 1 to 4), commercially available amorphous zinc oxide particles (SBC30N, SBC Co., Korea, hereinafter referred to as N-ZnO or Comparative Example 5), composite type Zinc oxide particles (Z-cote, BASF Co, Germany; hereinafter, C-ZnO or Comparative Example 6), plate-shaped zinc oxide particles (100XF, SAKAI, Comparative Example 7), plate-shaped zinc oxide particles (1000XF, SAKAI, Comparative Example 8) ), plate-shaped zinc oxide particles (2000XF, SAKAI, Comparative Example 9), nano-sized amorphous titanium oxide particles (MT-100TV, Tayca Co., Japan, hereinafter referred to as N-TiO ₂ or Comparative Example 10), micro-sized oxidation The particle shape and particle size distribution of the titanium particles (MP100, Tayca Co., Japan, hereinafter, M-TiO ₂ or Comparative Example 11) were analyzed.

SEM pictures and particle size distributions for the particles synthesized in Synthesis Example 1 are shown in FIGS. 4 and 5, respectively, and SEM pictures and particle size distributions for the particles synthesized in Synthesis Example 2 are shown in FIGS. 6 and 7, respectively, in Synthesis Example 3. SEM pictures and particle size distributions of the synthesized particles are shown in FIGS. 8 and 9, respectively, SEM pictures and particle size distributions for the particles synthesized in Synthesis Example 4 are shown in FIGS. 10 and 11, respectively, and for the particles synthesized in Synthesis Example 5 SEM pictures and particle size distribution are shown in FIGS. 12 and 13, respectively, SEM pictures and particle size distribution of the particles synthesized in Synthesis Example 6 are shown in FIGS. 14 and 15, respectively, and SEM pictures and particle size distribution of the particles synthesized in Synthesis Example 7 16 and 17, respectively, SEM pictures and particle size distributions for the particles synthesized in Synthesis Example 8 are in FIGS. 18 and 19, respectively, and SEM pictures and particle size distributions for the particles synthesized in Synthesis Example 9 are in FIG. 20, respectively. 21, the particle size distribution for the particles synthesized in Synthesis Example 10 is shown in FIG. 22, and the SEM image and particle size distribution for the particles synthesized in Synthesis Example 11 are shown in FIGS. 23 and 24, respectively, synthesized in Synthesis Example 12 The SEM picture of the coated particles is shown in FIG. 25, the SEM picture and particle size distribution of the particles synthesized in Synthesis Example 13 are shown in FIGS. 26 and 27, respectively, and the SEM picture and particle size distribution of the particles synthesized in Synthesis Example 14 are shown, respectively. 28 and 29 show.

On the other hand, SEM pictures and particle size distributions for the particles synthesized in Comparative Example 1 are shown in FIGS. 30 and 31, respectively, and SEM pictures and particle size distributions for the particles synthesized in Comparative Example 2 are shown in FIGS. 32 and 33, respectively. Comparative Example 3 SEM pictures and particle size distributions for the particles synthesized in FIGS. 34 and 35, respectively, SEM pictures and particle size distributions for the particles synthesized in Comparative Example 4 are shown in FIGS. 36 and 37, respectively, and SEM pictures for the particles of Comparative Example 5 38 and 39 for photos and particle size distribution, SEM photos and particle size distribution for Comparative Example 6 particles in FIGS. 40 and 41, respectively, and SEM photos and particle size distribution for Comparative Example 7 particles in FIGS. 42 and 43, respectively. 44 and 45 respectively for the SEM picture and particle size distribution of Comparative Example 8 particles, the particle size distribution for Comparative Example 9 particle size distribution in FIG. 46, and the SEM picture for Comparative Example 10 particle in FIG. 47, Comparative Example SEM pictures for 11 particles are shown in FIG. 48 , respectively. In addition, the particle size distribution results are shown in Table 1 below.

Microscopic shape and particle size distribution of inorganic particles Sample Microstructure (nm) particle size distribution Average
size Average
thickness aspect ratio d10
(mm) d[4,3]
(mm) d50
(mm) d90
(mm) d[4,3]
/size d90
/size d10
/thickness Synthesis Example 1 300 15 20.0 0.16 0.415 0.268 0.842 1.38 2.81 10.67 Synthesis Example 2 500 25 20.0 0.153 0.374 0.232 0.686 0.75 1.37 6.12 Synthesis Example 3 600 25 24.0 0.154 0.37 0.234 0.701 0.62 1.17 6.16 Synthesis Example 4 700 25 28.0 0.155 0.416 0.239 0.908 0.59 1.30 6.20 Synthesis Example 5 850 65 13.1 0.156 0.509 0.273 0.129 0.49 1.07 2.38 Synthesis Example 6 950 30 31.7 0.157 0.53 0.284 1.182 0.56 1.24 5.23 Synthesis Example 7 1050 30 35.0 0.157 0.583 0.336 1.359 0.40 1.29 5.23 Synthesis Example 8 850 15 57 0.153 0.545 0.254 1.313 0.64 1.54 10.2 Synthesis Example 9 900 45 20 0.154 0.551 0.262 0.950 0.61 1.06 3.49 Synthesis Example 10 850 12.5 68 0.157 0.66 0.436 1.571 0.776 1.86 12.56 Synthesis Example 11 250 20 12 0.153 0.335 0.231 0.565 1.34 2.26 7.65 Synthesis Example 12 850 15 57 0.153 0.545 0.254 1.313 0.64 1.54 10.2 Synthesis Example 13 800 15 53.3 0.156 0.565 0.271 1.358 0.71 1.70 10.0 Synthesis Example 14 800 15 53.3 0.156 0.866 0.275 2.501 1.08 3.13 10.4 Comparative Example 1 2000 100 20.0 - 16.1 13.5 31.4 8.05 15.70 - Comparative Example 2 1200 50 24.0 - 9.84 7.26 22.3 8.20 18.58 - Comparative Example 3 400 20 20.0 - 9.71 7.42 21.6 24.28 54.00 - Comparative Example 4 50 400 0.1 - 12.2 9.9 25.2 244.0 504.0 - Comparative Example 5 30 10 3.0 0.172 0.55 0.368 1.194 16.97 39.80 17.20 Comparative Example 6 30 80 0.4 0.142 0.212 0.196 0.301 7.07 10.03 1.78 Comparative Example 7 100 40 2.5 0.16 1.343 0.286 2.70 13.43 27.00 4.00 Comparative Example 8 700 250 2.8 0.1445 0.6245 0.2135 1.8555 0.89 2.65 0.58 Comparative Example 9 1600 500 3.2 1.273 4.217 3.863 7.482 2.64 4.68 2.55 d[4,3]: average volume weighted average

As shown in Table 1 and FIGS. 4 to 48, the zinc oxide particles synthesized according to Synthesis Examples 1 to 14 had an average particle size of 250 to 1050 nm, an average thickness of 12.5 to 65 nm, and an average thickness of The average size aspect ratio ranged from 12.5 to 68. In particular, the average volume-weighted average d _[4,3] ranges from 0.37 to 0.866 mm, the ratio of d _[4,3] to the average size ranges from 0.40 to 1.38, and the ratio of d ₉₀ to the average size ranges from 1.07 to 2.81. As a result, it was confirmed that the generated primary particles hardly agglomerated.

Meanwhile, in the case of the zinc oxide particles synthesized according to the acid neutralization method according to Comparative Examples 1 to 3, the average size was 1200 nm or more, d _[4,3] exceeded 9000 nm, and d ₉₀ was 2100 nm exceeds Accordingly, the ratio of d _[4,3] to the average size of the zinc oxide particles synthesized in Comparative Examples 1 to 3 is 8 or more, and the ratio of d ₉₀ to the average size exceeds 15, The particles were present in highly agglomerated form.

In addition, the zinc oxide particles synthesized according to Comparative Example 4 not only have an average thickness much larger than the average size, but also have d _[4,3] exceeding 12000 nm and d ₉₀ exceeding 9000 nm. Therefore, the ratio of d _[4.3] to the average size and the ratio of d ₉₀ to the average size were significantly large, 244.0 and 504.0, respectively, confirming that the primary particles were present in an excessively aggregated form.

The commercially available zinc oxide particles of Comparative Examples 5 to 9 also had an aspect ratio of 3.2 or less, and the ratio of d _[4.3] to the average size of each particle and the ratio of d ₉₀ to the average size were large. In addition, Comparative Example 10 (N-TiO ₂ ), which is a commercially available titanium oxide particle, mainly consists of amorphous particles having a size of several nm, and Comparative Example 11 (M-TiO ₂ ) has a size of several hundred nm to several um Eggplant was micropowder.

Example 2: Measurement of photoluminescence spectrum of inorganic particles

The photoluminescence spectra of the plate-shaped zinc oxide particles synthesized in Synthesis Example 1, Synthesis Example 8 to Synthesis Example 1 and Synthesis Example 12, respectively, and commercially available inorganic particles of Comparative Examples 5 to 8 were evaluated, and Peak intensity was measured. Peak intensities in the ultraviolet wavelength band (300 to 400 nm) and the visible-infrared wavelength band (500 to 1000 nm) were separately measured. The photoluminescence spectrum was measured three times for each inorganic particle, and the results were averaged. The measurement results are shown in Table 2 and FIG. 49 below.

Peak intensity in the photoluminescence spectrum of inorganic particles Sample 300-400 nm peak intensity (a) 500-1000 nm
peak intensity (b) peak intensity ratio
(b/a) Comparative Example 5 84,468 1,669,809 19.768 Comparative Example 6 335,334 3,067,906 9.119 Comparative Example 7 693,124 2,384,587 3.440 Comparative Example 8 379,248 2,354,890 6.209 Synthesis Example 1 993,089 1,157,018 1.165 Synthesis Example 8 1,019,173 173,389 0.170 Synthesis Example 9 424,799 296,400 0.698 Synthesis Example 10 888,710 418,229 0.471 Synthesis Example 12 2,469,585 613,255 0.248

As shown in Table 2 and FIG. 49, the peak intensity of the plate-like zinc oxide particles synthesized in Synthesis Example is increased in the ultraviolet wavelength band, which is the intrinsic emission wavelength band, compared to the emission intensity in the visible-infrared wavelength band. This result seems to be because the aspect ratio of the plate-like zinc oxide particles synthesized in the present invention greatly increased, the specific surface area of the polar face widened, and surface defects such as oxygen vacant lattice points decreased.

Example 3: Evaluation of physical properties of cosmetics formulated with single inorganic particles

(1) Light-transmittance measurement

A mixture of plate-like zinc oxide particles synthesized in Synthesis Examples 4 to 10 and Synthesis Example 12 (hereinafter referred to as "P-ZnO"), commercially available inorganic powders, Z-Cote (C-ZnO), MT- Oil-in-water cosmetics were prepared by adding 100TV (N-TiO ₂ ) MP100 (M-TiO ₂ ) in an amount of 15% by weight, respectively, as shown in Table 3 below.

cosmetic formulation Phase Material Composition (% by weight)
powder (dispersed phase)
inorganic particles ^* 15 Cetiol CC (dispersion solvent-ester oil) 9 SPAN 120-LQ-RB (Dispersant-Surfactant) One


oil phase Cetiol CC (Yesester Oil) 3 C12-15 Alkylbenzoate (Frisolv TNQ) (ester oil) 5 KAX 99 (Salacos 99) (ester oil) 3 ABIL EM-90 (ester oil) 2 Cerestin Wax (melting point 75-80℃) 2 Bees Wax (melting point 65-70℃) 0 or 3
Awards Purified water 47.56 (44.56 with Bees Wax) EDTA-2Na (chelating agent) 0.04 NaCl (viscosity and W/O stabilizer) One 1,3-butylne glycol (moisturizer) One Glycerin (moisturizer) 11 additive Phenoxyethanol (preservative) 0.4 ^* : plate-shaped zinc oxide particles (P-ZnO; Examples 4-10 and 12); C-ZnO (Comparative Example 6); N-TiO ₂ (Comparative Example 10); M-TiO ₂ (Comparative Example 11)

Each cosmetic sample was applied on a PMMA substrate (50 mm x 50 mm), a standard substrate for measuring sunscreen in Europe, by injecting 10 mL of the prepared sample using a syringe, dividing it into about 100 spots evenly over the entire surface of the substrate. The application was completed by scrubbing the applied sample while wearing latex gloves. Excluding the sample remaining in the latex glove, the final applied sample amount was maintained at about 0.05 g, and the light-transmittance was measured. An agitator (Homogenizer disper model 2.5, PRIMX, Netherland) and a homo-mixer (PL-HMZ30DN, Poonglim Co., Korea) were sequentially used so that the cosmetic formulation ingredients could be perfectly mixed during the formulation process. A spectrometer (LAMBDA 750 PerkinElmer, USA) capable of measuring light-transmittance in the wavelength range from 300 to 1100 nm ultraviolet to near-infrared is used to evaluate the optical properties of the sample coated with cosmetic ingredients including each inorganic particle. did The UV blocking rate (%) was expressed numerically by subtracting the average transmittance (%) of the UV region of 300 to 400 nm from 100 in the measured spectrum. The light transmittance measurement results are shown in FIG. 50, and the UV blocking rate measurement results are shown in Table 4 below.

M-TiO ₂ powder particles with large particle sizes ranging from hundreds of nm to several um showed relatively low transmittance, that is, high blocking effect, in the visible and infrared regions, but very high transmittance of more than 30% in the ultraviolet region. There was little to no UV protection effect. On the other hand, C-ZnO and N-TiO ₂ particles, including particles with a particle size of tens of nm or less, showed high blocking effect in the ultraviolet region, but showed about 80% transmittance in the infrared region, resulting in heat loss due to infrared shielding. It was expected that the blocking effect would not be high. On the other hand, the plate-like zinc oxide particles synthesized in Example, P-ZnO, showed much more blocking effect than M-TiO ₂ powder in the ultraviolet region, and better blocking effect than fine powders such as N-ZnO and N-TiO ₂ in the infrared region. showed effect. The reason for the relatively good blocking effect in the ultraviolet and infrared regions is that the P-ZnO plate-shaped zinc oxide particles synthesized in the present invention have a dimension close to the um range in the length direction and a dimension of several tens of nm in the thickness direction. to be.

(2) Cloudiness and heat blocking effect

The cosmetics formulated according to Table 3 were analyzed for cloudiness (L value) and heat blocking effect. The formulated sample was applied by sliding it to a constant thickness of 60 um using an applicator (1241876, BYK Co., Germany) on sliding glass to measure the application properties and formulation stability. Applying properties and initial formulation stability were evaluated by relatively comparing the uniformly applied area and uniformity on the glass substrate. In addition, in order to further determine the long-term stability of the formulation, the occurrence of separation between the layers of the formulated cream was observed one week after completion of the formulation.

The cloudiness of the cosmetic sample containing the applied inorganic substance was measured by applying 0.1 g of cream to the same area (5 × 5 cm ² ) on artificial leather (draft wood color, L* value of 47) with pores in a color similar to that of the skin. After coating, it was measured numerically by a color difference meter (LAMBDA 750, PerkinElmer, USA). In order to evaluate the heat blocking effect, a 400W Xe lamp was operated at a distance of 12 cm, and artificial skin with a temperature sensor inserted was placed under the cosmetic ingredient-coated PMMA substrate sample and the bare PMMA substrate. The larger the temperature difference between the two measured samples, the higher the heat shielding effect can be evaluated. The analysis results according to this embodiment are shown in FIGS. 51 and 52 and Table 4.

ΔT means the temperature difference measured between the substrate to which each formulated sample is applied and the artificial skin under the uncoated substrate, and the higher the value, the higher the heat shielding effect. As shown in FIG. 49, N-TiO ₂ had a formulation stability problem and phase separation occurred, which caused inorganic particles to agglomerate due to a relatively large specific surface area compared to the same weight. and separation of the oil phase appears to have occurred. M-TiO ₂ had good formulation stability and heat blocking effect, but had a high turbidity (L value) of 68, so it looked white to the naked eye. On the other hand, the sample containing the plate-like zinc oxide particles (P-ZnO) synthesized in Example had a better thermal blocking effect than the sample containing C-ZnO and N-TiO ₂ particles, and the above-described analysis of the light-blocking effect matches In particular, the samples containing the plate-like zinc oxide particles synthesized in Examples had the best spreadability and formulation stability. Excellent spreadability is related to the plate-like microstructure, and formulation stability means that aggregation hardly occurs between particles.

Blend of inorganic particles Sample P-ZnO N-ZnO
(SBC30N) C-ZnO
(Z-cote) N—TiO ₂ M—TiO ₂ UV
Block rate _*
blue light
Block rate ^** Heat rejection rate ^*** One 15 - - - - 96.3% 47% 34.6% 2 - 15 - - - 88.2% 21% 14.2% 3 - - 15 - - 93.1% 36% 23.8% 4 - - - 10 - 94.8% 42% 24.9% 5 - - - - 5 67.8% 40% 36.3% ^* : 300-400 nm; **: 380-500 nm; ^*** : 300-1100 nm

Example 4: Evaluation of Physical Properties of Cosmetics Formulated with Inorganic Particles

As shown in Table 5 below, cosmetics formulated in the same manner as shown in Table 3 were prepared, except that the content of the total inorganic particles was adjusted to 15% by weight. Each sample was analyzed for light transmittance, opacity and heat shielding effect according to the same procedure as in Example 3.

Blend of inorganic particles Sample C-ZnO P-ZnO M—TiO ₂ UV blocking rate ^* Heat rejection rate ^** One 15 - - 96.6% 23.8% 2 7.5 7.5 - 98.9% 26.9% 3 5 10 99.5% 32.5% 4 12.5 2.5 - 96.4% 25.5% 5 7.5 5 2.5 98.1% 34.5% 6 5 7.5 2.5 96.7% 34.7% ^* : 300-380 nm; ^** : 300-1000 nm

53 shows the results of measuring the UV blocking rate and the thermal blocking rate for cosmetic samples formulated by blending inorganic particles according to this embodiment. For comparison, when an organic sunscreen commercial product (LAVIDA sun solution, Coreana Cosmetics Co., Korea) was measured under the same conditions and system, the sunscreen rate and heat blocking effect were 96.5% and 2.5℃, respectively. When P-ZnO prepared according to the present invention was blended with C-ZnO, the UV and heat blocking effects were greatly increased. In addition, when C-ZnO is mixed with P-ZnO and M-TiO ₂ , the heat shielding effect is further improved than when only P-ZnO is mixed with C-ZnO.

54 and 55 show the results of white turbidity change, spreadability and formulation stability of cosmetic samples formulated by blending inorganic particles according to this embodiment. It was confirmed that application and formulation stability were improved when P-ZnO and optionally M-TiO ₂ were blended with C-ZnO.

Example 5: Evaluation of Physical Properties of Cosmetics Formulated with Inorganic Particles

As shown in Table 6 below, cosmetics formulated in the same manner as shown in Table 3 were prepared, except that the content of the total inorganic particles was adjusted to 15% by weight. Each sample was analyzed for light transmittance, opacity and heat shielding effect according to the same procedure as in Example 3.

Blend of inorganic particles Sample N—TiO ₂ P-ZnO M-TiO2 UV blocking rate ^* Heat rejection rate ^** One 15 - - 96.6% 24.9% 2 7.5 7.5 - 97.3% 27.0% 3 5 10 99.4% 31.4% 4 12.5 2.5 - 99.3% 39.5% 5 7.5 5 2.5 99.3% 41.5% 6 5 7.5 2.5 98.7% 37.3% ^* : 300-380 nm; ^** : 300-1000 nm

56 shows the results of measuring the UV blocking rate and the thermal blocking rate for cosmetic samples formulated by blending inorganic particles according to this embodiment. When N-TiO ₂ was blended with P-ZnO prepared according to the present invention, the UV and heat blocking effects were greatly increased. On the other hand, when P-ZnO and M-TiO ₂ are blended with N-TiO ₂ , the heat shielding effect is further improved than when P-ZnO is blended with N-TiO ₂ alone.

57 and 58 show the results of change in opacity, spreadability and formulation stability of cosmetic samples formulated by blending inorganic particles according to this embodiment. When N-TiO ₂ was mixed with P-ZnO and optionally M-TiO ₂ , it was confirmed that the spreadability and formulation stability were improved.

59 shows the result of analyzing the relationship between the chromaticity and heat blocking effect of the cosmetic sample according to the present embodiment. In general, cloudiness and heat shielding effect increase proportionally, but when N-TiO ₂ particles are combined with the P-ZnO particles synthesized according to the present invention, the heat shielding effect is increased while cloudiness is reduced. In addition, as confirmed in FIGS. 53 to 55, the UV blocking rate and spreadability were improved in this section, and overall meaningful performance improvement was achieved while mixing P-ZnO particles in a mixed formulation based on N-TiO2 particles. it means.

Example 6: Evaluation of Physical Properties of Cosmetics Formulated with Inorganic Particles

As shown in Table 7 below, cosmetics formulated in the same manner as shown in Table 3 were prepared, except that the content of the total inorganic particles was adjusted to 15% by weight. Each sample was analyzed for light transmittance, opacity and heat shielding effect according to the same procedure as in Example 3.

Blend of inorganic particles Sample N-ZnO P-ZnO M-TiO2 UV blocking rate ^* Heat rejection rate ^** One 15 - - 92.3% 14.2% 2 7.5 7.5 - 96.4% 25.5% 3 5 10 95.9% 26.1% 4 12.5 2.5 - 93.2% 23.1% 5 7.5 5 2.5 96.7% 34.7% 6 5 7.5 2.5 95.6% 33.7% ^* : 300-380 nm; ^** : 300-1000 nm

60 shows the results of measuring the UV blocking rate and the thermal blocking rate for cosmetic samples formulated by blending inorganic particles according to this embodiment. When N-ZnO was blended with P-ZnO prepared according to the present invention, the UV and heat blocking effects were greatly increased. On the other hand, when P-ZnO and M-TiO ₂ are blended with N-ZnO, the heat shielding effect is further improved than when P-ZnO is blended with N-ZnO ₂ alone. 61 and 62 show the results of change in opacity, spreadability and formulation stability for cosmetic samples formulated by blending inorganic particles according to this embodiment. When N-ZnO was mixed with P-ZnO and optionally M-TiO ₂ , it was confirmed that spreadability and formulation stability were improved.

Example 7: Evaluation of Physical Properties of Cosmetics Formulated with Inorganic Particles

As shown in Table 8 below, cosmetics formulated in the same manner as shown in Table 3 were prepared, except that the content of the total inorganic particles was adjusted to 11% by weight. Each sample was analyzed for light transmittance and heat blocking effect according to the same procedure as in Example 3. The cosmetic composition in which the planar zinc oxide particles synthesized according to the present invention and other inorganic particles were mixed showed excellent light blocking rate and heat blocking rate.

Blend of inorganic particles Sample N—TiO ₂ P-ZnO N-ZnO M—TiO ₂ ASC ^* UV block rate ^** Heat rejection rate ^*** One 6.6 ^**** 4.4 - - - 98.7% 25.6% 2 6.6 ^****** 4.4 - - - 97.6% 27.2% 3 5 3.9 1.6 0.5 - 99.2% 32.7% 4 5 3.9 - 0.5 1.6 95.4% 30.5% ^* : columnar TiO ₂ ; ^** : 300-380 nm; ^*** : 300–1000 nm; ^**** : Liquid; ^***** : Powder

Example 8: Evaluation of Physical Properties of Cosmetics Formulated with Inorganic Particles

As shown in Table 9 below, cosmetics formulated in the same manner as shown in Table 3 were prepared, except that the content of the total inorganic particles was adjusted to 15% by weight. Each sample was analyzed for light transmittance and heat blocking effect according to the same procedure as in Example 3. The cosmetic composition synthesized according to the present invention alone or in combination with zinc oxide platelets and other inorganic particles showed excellent light and heat blocking rates.

Blend of inorganic particles Sample Synthesis Example 1 P-ZnO N—TiO ₂ C-ZnO N-ZnO UV blocking rate ^* Heat rejection rate ^** One 15 - - - - 97.6% 29.4% 2 10 - 5 - - 98.6% 27.1% 3 - 10 5 - - 99.0% 38.6% 4 10 - - 5 - 99.8% 31.7% 5 3 10 - 2 96.7% 25.8% ^* : 300-380 nm; ^** : 300-1000 nm

Example 9: Zeta Potential Measurement of Inorganic Particles

The inorganic particles synthesized in Synthesis Example 8 were dispersed in water to measure zeta potential. In addition, the surface-treated inorganic particles according to Synthesis Example 12 were dispersed in oil to measure zeta potential. For comparison, after dispersing untreated N-ZnO particles (SBC-30N) and C-ZnO particles (Z-cote) particles in water, the zeta potential and surface-treated N-ZnO particles in the same manner as in Synthesis Example 12 After dispersing the particles and C-ZnO particles in oil, the zeta potentials were measured, respectively. The measurement results are shown in Table 10 below. It was confirmed that a large number of O ⁻ ions remained on the surface of the plate-like zinc oxide particles synthesized according to the present invention, and thus the surface defects were small.

Zeta Potential of Inorganic Particles Sample no surface treatment
(water dispersion) silicone surface treatment
(oil dispersion) Synthesis Example 8 -20.0 mV - Synthesis Example 12 - -20.5 mV N-ZnO 18.9mV -16.6 mV C-ZnO 19.4 mV -111.2 mV

Example 10: Antibacterial evaluation of powdered zinc oxide particles

(1) Primary antibacterial evaluation

In Synthesis Example 12, an O/W formulation (0.3 mg each) containing 15% by weight of plate-shaped zinc oxide particles coated with a silane coupling agent and SBC30N (N-ZnO) and Z-cote (C-ZnO) particles was prepared. It was put in 50 mL of phosphate buffer solution (pH 7.2), and shaken for 1 hour in a shaker set at 35 ± 1 ° C. Escherichia coli (ATCC 25922) was inoculated at 4.2 X 10 ⁵ CFU/mL, diluted to a concentration as shown in Table 8 below, cultured for 15 hours or more, and antimicrobial activity was evaluated according to the ASTM E2149-13a standard. Table 11 shows the results of the primary antibacterial evaluation. It was confirmed that the plate-shaped zinc oxide particles had improved antibacterial properties compared to other commercially available inorganic particles.

Antibacterial evaluation of platelet zinc oxide particles density
(mM) Synthesis Example 12 N-ZnO C-ZnO Viable cell count (CFU/mL) decrease rate Viable cell count (CFU/mL) decrease rate Viable cell count (CFU/mL) decrease rate 0.6 2.8 X 10 ⁴ 93.3% 4.0 X 10 ⁴ 90.5% 5.6 X 10 ⁴ 86.7% 0.06 4.8 X 10 ⁴ 88.6% 5.6 X 10 ⁴ 86.7% 8.0 X 10 ⁴ 81.0%

(2) Secondary antibacterial evaluation

The O/W formulation (0.3 mg each) containing 15% by weight of each of the plate-like zinc oxide particles synthesized in Synthesis Example 12 and the N-ZnO particles was put into 50 mL of a phosphate buffer solution (pH 7.2), set at 35 ± 1 ° C. Shake for 1 hour on a shaker. Staphylococcus aureus ( S. aureus ) was inoculated at 8 X 10 ⁴ CFU/mL after 5 minutes of shaking. After diluting to the concentration shown in Table 10 and incubating for more than 15 hours, the antimicrobial activity was evaluated according to the ASTM E2149-13a standard. Table 12 shows the results of the secondary antibacterial evaluation. It was confirmed that the plate-shaped zinc oxide particles had improved antibacterial properties compared to other commercially available inorganic particles.

Antibacterial evaluation of platelet zinc oxide particles density
(mM) Synthesis Example 12 N-ZnO Viable cell count (CFU/mL) decrease rate Viable cell count (CFU/mL) decrease rate 1.2 1.3 X 10 ⁴ 83.7% 1.7 X 10 ⁴ 78.4% 0.6 4.8 X 10 ⁴ 88.6% > 2.0 X 10 ⁴ <75% 0.12 3.9 X 10 ⁴ 51.6% 4.3 X 10 ⁴ 45.7% 0.06 4.5 X 10 ⁴ 43.4% 6.7 X 10 ⁴ 16.2%

(3) Evaluation of tertiary antibacterial properties

The plate-like zinc oxide particles synthesized in Synthesis Example 1, Synthesis Example 8, and Synthesis Example 12 were formulated in an O/W form, or the antibacterial properties of the powdered zinc oxide particles were evaluated. The antimicrobial measurement results are shown in Table 13 below. Antibacterial properties of the plate-like zinc oxide particles were improved not only in the O/W formulation but also in the particle state.

Antibacterial evaluation of platelet zinc oxide particles Sample exam
standard strain particle
(content, %) formulation antibacterial activity
(log) Early
number of germs 24 hours elapsed
(Blank) One ASTM E2149-13a Escherichia coli Synthesis Example 8 ^* (15.0) O/W 3.6 210,000 30
(130,000) 2 ASTME2149-14a Escherichia coli Synthesis Example 1 ^*
(15.0) O/W 3.7 250,000 30
(170,000) 3 ASTME2149-14a Escherichia coli Synthesis Example 1 ^**
(15.0) O/W 3.7 25,000 30
(170,000 4 ASTME2149-15a Escherichia coli Synthesis Example 8
(100) powder 3.6 210,000 30
(130,000) ^* : 0.3 mg; ^** : 1.0 mg;

Example 11: Antibacterial evaluation of zinc oxide particles formulated in film form

The plate-like zinc oxide particles synthesized in Synthesis Example 1, Synthesis Example 8, and Synthesis Example 12 were coated on a polymer film at the concentrations shown in Tables 14 to 18 below, and formulated into a film form. The strains shown in Tables 14 to 18 were inoculated and the number of viable cells was measured after 24 hours to evaluate antibacterial properties. In Tables 14 to 18, LDPE represents low-density polyethylene, PP represents polypropylene, ABS represents acrylonitrile butadiene styrene, PVC represents polyvinyl chloride, EPP represents expanded polypropylene, and PET represents polyethylene terephthlate. LDPE was used for films or zipper bags, ABS and EPP for automobile parts, PVC for medical tubes, silicone for water purifier parts, coating liquid for can coating, PP for webbing and yarn, and PET for nonwoven fabric or yarn.

Antibacterial evaluation of formulated platelet zinc oxide particles Sample exam
standard strain particle
(content, %) film
(um) antibacterial activity
(log) Early
number of germs 24 hours elapsed
(Blank) One JIS ^* Hwangpobacteria Synthesis Example 12
(0.25) LDPE
(100) 2.1 14,000 200
(27,000) 2 JIS Escherichia coli Synthesis Example 12
(0.25) LDPE
(100) 3.5 14,000 250
(920,000) 3 JIS Hwangpobacteria SBC30N
(0.25) LDPE
(100) 0.5 14,000 7,900
(27,000) 4 JIS Escherichia coli SBC30N
(0.25) LDPE
(100) 3.4 14,000 320
(920,000) 5 JIS Hwangpobacteria Synthesis Example 8
(1.00) LDPE
(25) 4.5 16,000 One
(24,000) 6 JIS Hwangpobacteria Synthesis Example 8
(0.50) LDPE
(25) 4.5 16,000 One
(24,000) 7 JIS Escherichia coli Synthesis Example 8
(0.50) LDPE
(25) 6.2 14,000 One
(1,100,000) 8 JIS Hwangpobacteria Synthesis Example 8
(0.25) LDPE
(25) 4.5 16,000 1,100
(24,000) 9 JIS Escherichia coli Synthesis Example 8
(0.25) LDPE
(25) 3.0 14,000 One
(1,100,000) 10 JIS Hwangpobacteria SBC30N
(1.00) LDPE
(25) 4.5 17,000 One
(24,000) 11 JIS Hwangpobacteria SBC30N
(0.50) LDPE(25) 4.5 17,000 One
(24,000) 12 JIS Escherichia coli SBC30N(
0.50) LDPE
(25) 3.3 14,000 539
(1,100,000) 13 JIS Hwangpobacteria SBC30N
(0.25) LDPE
(0.25) 3.4 17,000 9
(24,000) 14 JIS Escherichia coli SBC30N
(0.25) LDPE
(0.25) 3.5 14,000 310
(1,100,000) 15 JIS Hwangpobacteria 3 antibacterial agent
(1.0) LDPE 4.6 14,000 One
(24,000) 16 JIS Escherichia coli 3 antibacterial agent
(1.00) LDPE 6.2 14,000 One
(1,100,000) ^* : JIS Z 2810:2010

Antibacterial evaluation of formulated platelet zinc oxide particles Sample exam
standard strain particle
(content, %) film antibacterial activity
(log) Early
number of germs 24 hours elapsed
(Blank) One JIS ^* Hwangpobacteria AGZ330
(1.0) ABS 2.9 17,000 27
(26,000) 2 JIS Escherichia coli AGZ330
(1.0) ABS 6.2 14,000 One
(1,100,000) 3 JIS Hwangpobacteria VZ600
(1.0) ABS 0 17,000 31,000
(26,000) 4 JIS Escherichia coli VZ600
(1.0) ABS 3.0 14,000 870
(1,100,000) 5 JIS Hwangpobacteria Synthesis Example 8 (1.0) ABS 4.6 17,000 One
(26,000) 6 JIS Escherichia coli Synthesis Example 8 (1.0 ABS 6.2 14,000 One
(1,100,000) 7 JIS Hwangpobacteria SBC30N
(1.0) ABS 4.6 17,000 One
(26,000) 8 JIS Escherichia coli SBC30N
(1.0) ABS 4 14,000 110
(1,100,000) 9 JIS Hwangpobacteria Synthesis Example 8 (1.0) PVC 4.6 17,000 One
(26,000) 10 JIS Escherichia coli Synthesis Example 8 (1.0) PVC 2.8 17,000 1,500
(1,100,000) 11 JIS Pneumococcus Synthesis Example 8 (1.0) PVC 3.2 17,000 160
(260,000) 12 JIS Pseudomonas aeruginosa Synthesis Example 8 (1.0) PVC 3.5 17,000 170
(230,000) 13 JIS pneumococci Synthesis Example 12 (1.0) PVC 3.1 17,000 95
(260,000) 14 JIS Pseudomonas aeruginosa Synthesis Example 12 (1.0) PVC 3.2 17,000 120
230,000) 15 JIS Hwangpobacteria Synthesis Example 8 (0.25) PVC 4.6 14,000 One
(26,000) 16 JIS Escherichia coli Synthesis Example 8 (0.25) PVC 2.8 14,000 1,600
(1,100,000) ^* : JIS Z 2810:2010

Antibacterial evaluation of formulated platelet zinc oxide particles Sample exam
standard strain particle
(content, %) film antibacterial activity
(log) Early
number of germs 24 hours elapsed
(Blank) One JIS ^* Hwangpobacteria Synthesis Example 8 (1.0) silicon 4.5 14,000 One
(24,000) 2 JIS Escherichia coli Synthesis Example 8 (1.0) silicon 3.4 14,000 410
(1,100,000) 3 JIS Hwangpobacteria Synthesis Example 8 (0.25) silicon 1.8 14,000 350
(24,000) 4 JIS Escherichia coli Synthesis Example 8 (0.25) silicon 3.2 14,000 640
(1,100,000) 5 JIS Hwangpobacteria Synthesis Example 12 (1.0) silicon 4.5 14,000 One
(24,000) 6 JIS Escherichia coli Synthesis Example 12 (1.0) silicon 6.2 14,000 One
(1,100,000) 7 JIS Hwangpobacteria Synthesis Example 12 (0.25) silicon 4.5 14,000 One
(24,000) 8 JIS Escherichia coli Synthesis Example 12 (0.25) silicon 6.2 14,000 One
(1,100,000) 9 JIS Hwangpobacteria platinum hardener silicon 0 14,000 39,000 (24,000) 10 JIS Escherichia coli platinum hardener silicon 0.3 14.000 510,000
(1,100,000) 11 JIS Hwangpobacteria - silicon 0 14,000 53,000 (24,000) 12 JIS Escherichia coli - silicon 1.3 14,000 46,000 (1,100,000) 13 JIS Hwangpobacteria SBC30N
(1.0) silicon 3.4 14,000 8
(24,000) 14 JIS Escherichia coli SBC30N
(1.0) silicon 0.3 14,000 500,000
(1,100,000) 15 JIS Hwangpobacteria SBC30N
(0.25) silicon 0.9 14,000 2,500
(24,000) 16 JIS Escherichia coli SBC30N
(0.25) silicon 0 14,000 1,100,000
(1,100,000) ^* : JIS Z 2810:2010

Antibacterial evaluation of formulated platelet zinc oxide particles Sample exam
standard strain particle
(content, %) film antibacterial activity
(log) Early
number of germs 24 hours elapsed
(Blank) One JIS ^* Hwangpobacteria Synthesis Example 8 (0.25) coating liquid 4.5 15,000 One
(25,000) 2 JIS Escherichia coli Synthesis Example 8 (0.25) coating liquid 4.3 17,000 50
(1,100,000) 3 JIS Hwangpobacteria Synthesis Example 8 (0.5) coating liquid 4.5 15,000 One
(25,000) 4 JIS Escherichia coli Synthesis Example 8 (0.5) coating liquid 6.2 15,000 One
(1,100,000) 5 JIS Hwangpobacteria Synthesis Example 8 (0.3) EPP 1.2 17,000 1,300
(25,000) 6 JIS Escherichia coli Synthesis Example 8 (0.3) EPP 4.1 14,000 79
(1,100,000) 7 JIS Hwangpobacteria Synthesis Example 8 (1.0) EPP 4.5 17,000 One
(25,000) 8 JIS Escherichia coli Synthesis Example 8 (1.0) EPP 3 14,000 1,000
(1,100,000) 9 JIS Hwangpobacteria Synthesis Example 12 (0.3) EPP 3.4 17,000 8
(25,000) 10 JIS Escherichia coli Synthesis Example 12 (0.3) EPP 3.8 14,000 160
(1,100,000) 11 JIS Hwangpobacteria Synthesis Example 12 (1.0) EPP 2.2 17,000 130
(25,000) 12 JIS Escherichia coli Synthesis Example 12 (1.0) EPP 3.3 14,000 500
(1,100,000) ^* : JIS Z 2810:2010

Antibacterial evaluation of formulated platelet zinc oxide particles Sample exam
standard strain particle
(content, %) film antibacterial activity
(log) Early
number of germs 24 hours elapsed
(Blank) One KS ^* Hwangpobacteria - PP 2.4 18,000 40,000 (9,300,000) 2 KS Hwangpobacteria Synthesis Example 12 (0.23) PP 6.0 18,000 10
(9,800,000) 3 KS pneumococci Synthesis Example 12 (0.23) PP 6.6 19,000 10
(38,000,000) 4 KS Hwangpobacteria Synthesis Example 12 (0.30) PP 6.0 18,000 10
(9,800,000) 5 KS pneumococci Synthesis Example 12 (0.30) PP 6.6 19,000 10
(38,000,000) 6 KS Hwangpobacteria Synthesis Example 8 (1.0) PET 6.0 18,000 10
(9,800,000) 7 KS pneumococci Synthesis Example 8 (1.0) PET 6.6 19,000 10
(38,000,000) 8 KS Hwangpobacteria Synthesis Example 12 (0.3) PP 6.0 18,000 10
(9,800,000) 9 KS pneumococci Synthesis Example 12 (0.3) PP 2.8 22,000 56,000
(38,000,000) 10 KS Hwangpobacteria Synthesis Example 12 (0.6) PP 6.0 18,000 10
(9,800,000) 11 KS pneumococci Synthesis Example 12 (0.6) PP 6.6 22,000 10
(38,000,000) 12 KS Hwangpobacteria Synthesis Example 8 (0.3) PP 6.0 18,000 10
(9,800,000) 13 KS pneumococci Synthesis Example 8 (0.3) PP 6.6 22,000 10
(38,000,000) 14 KS Hwangpobacteria Synthesis Example 8 (0.6) PP 6.0 18,000 10
(9,800,000) 15 KS pneumococci 8 (0.6) to composites PP 6.6 22,000 10
(38,000,000) 16 KS Hwangpobacteria - PET 2.7 17,000 17,000 (9,300,000) 17 KS Hwangpobacteria Synthesis Example 12 (0.25) PET 4.2 17,000 620
(9,300,000) 18 KS pneumococci Synthesis Example 12 (0.25) PET 4.0 22,000 2,600
(27,000,000) 19 KS Hwangpobacteria Synthesis Example 12 (0.5) PET 6.0 17,000 10
(9,300,000) 20 KS pneumococci Synthesis Example 12 (0.5) PET 6.4 22,000 10
(27,000,000) ^* : KS K 0693:2016

Example 12: Evaluation of antiviral activity

The plate-shaped zinc oxide particles synthesized in Synthesis Example 8 were formulated by coating on a polymer film, and corona virus (CoV, 229E, GF, titer 2.5 X 10 ⁵ PFU) was inoculated, and 1 hour later, the PFU of the virus was measured. The measurement results are shown in Figs. 63 and 64. The surviving virus was 6.7 X 10 ² PFU, and more than 99% of the virus was killed compared to the inoculated amount.

In the above, the present invention has been described based on exemplary embodiments and examples of the present invention, but the present invention is not limited to the technical idea described in the above embodiments and examples. Rather, those skilled in the art to which the present invention pertains can easily make various modifications and changes based on the above-described embodiments and examples. However, it is clear from the appended claims that all of these modifications and changes fall within the scope of the present invention.

100: zinc oxide particles
200: zinc air battery system 210: negative electrode
220: anode 230: electrolyte
240: separator

Claims (25)

discharging the zinc-air battery to obtain an electrolyte containing an anionic zinc compound and zinc oxide;
diluting the electrolyte by adding a diluting solvent to the obtained electrolyte; and
A method for producing plate-like zinc oxide particles comprising the step of forming zinc oxide crystals by reacting a zinc salt with the diluted electrolyte solution,
The plate-shaped zinc oxide particles have an average particle size of 200 to 1200 nm and an average particle thickness of 10 to 80 nm, and an aspect ratio of the average particle size to the average particle thickness is 10:1 to 70:1, , A method for producing plate-like zinc oxide particles wherein the ratio of particle size distribution d ₉₀ to the average particle size (d ₉₀ /average particle size) is 1.0 to 3.5. delete The method of claim 1, wherein the forming of the zinc oxide crystals is performed in the presence of a salt. 4. The method of claim 3, wherein the salt is selected from the group consisting of C _{1 -C 10 organic acid salts of alkali metals, C 1 -C 10 organic acid} salts of alkaline earth metals, and combinations thereof. How to. The method of claim 1, further comprising adding a salt to the diluted electrolyte solution between diluting the electrolyte solution and forming the zinc oxide crystals. The method of claim 1, further comprising a step of surface treating the synthesized plate-like zinc oxide crystals after the step of forming the zinc oxide crystals. discharging the zinc-air battery to obtain an electrolyte containing an anionic zinc compound and zinc oxide;
diluting the electrolyte by adding a diluting solvent to the obtained electrolyte; and
A method for producing plate-like zinc oxide particles comprising the step of forming zinc oxide crystals by reacting a zinc salt with the diluted electrolyte solution,
In the photoluminescence spectrum of the zinc oxide particles, the ratio of the emission peak in the wavelength range of 500 to 1000 nm and the emission peak in the wavelength range of 300 to 400 nm is 0.1 to 1.5 to prepare plate-like zinc oxide particles. How to. The method of claim 1, wherein the diluting solvent used in the step of diluting the electrolyte solution is distilled water. The method of claim 1, wherein in the step of diluting the electrolytic solution, the diluting solvent is used in a volume ratio of 1 to 50 times that of the obtained electrolytic solution. The method of claim 1, wherein the electrolyte solution diluted by adding the diluent solvent contains 2 to 10% (w/v) of the electrolyte. The method of claim 1, wherein in the step of forming the zinc oxide crystals, the zinc salt is added at a concentration of 0.1 to 2.0 M. The method of claim 1, wherein the zinc salt is selected from the group consisting of organic acid zinc, inorganic acid zinc, and combinations thereof. 13. The method of claim 12, wherein the organic acid zinc comprises C ₁ -C ₂₀ organic acid zinc. 13. The method of claim 12, wherein the organic acid zinc is zinc carboxylate selected from the group consisting of zinc formate, zinc acetate, zinc lactate, zinc propionate, zinc gluconate, zinc benzoate, and combinations thereof. method. 13. The method of claim 12, wherein the organic acid zinc is polyvalent zinc carboxylate selected from the group consisting of zinc oxalate, zinc malonate, zinc tartrate, zinc citrate, zinc succinate, and combinations thereof. 4. The method of claim 3, wherein the salt is an alkali metal salt or alkaline earth metal salt of a single carboxylic acid selected from the group consisting of formic acid, acetic acid, lactic acid, propionic acid, gluconic acid, benzoic acid, and combinations thereof. manufacturing method. The method of claim 3, wherein the salt is an alkali metal salt or an alkaline earth metal salt of a polyvalent carboxylic acid selected from the group consisting of oxalic acid, malonic acid, tartaric acid, citric acid, succinic acid, and combinations thereof. method. The method of claim 3, wherein the salt is added at a concentration of 0.01 to 0.5 mM. The method of claim 5, wherein the salt is dissolved in water at a concentration of 5 to 40% (w/v). The method of claim 1, wherein the zinc salt is added to the diluted electrolyte solution at a temperature of 60 to 95 ° C, and the reaction between the zinc salt and the diluted electrolyte solution is carried out at a temperature of 50 to 95 ° C. manufacturing method. The method of claim 1, wherein in the step of forming the zinc oxide crystals, the zinc salt is added to the diluted electrolyte solution at a rate of 2.0 to 5 L/minute. The platelet zinc oxide according to claim 6, wherein the surface treatment comprises treating the surface of the platelet zinc oxide particles with a surface treatment agent in an amount of 0.1 to 20% by weight based on the total weight of the surface-treated zinc oxide platelets. How to make particles. discharging the zinc-air battery to obtain an electrolyte containing an anionic zinc compound and zinc oxide;
diluting the electrolyte by adding a diluting solvent to the obtained electrolyte; and
A method for producing plate-like zinc oxide particles comprising the step of forming zinc oxide crystals by reacting a zinc salt with the diluted electrolyte solution,
The plate-like zinc oxide particles have an average particle size of 200 to 1100 nm, an average thickness of 12.5 to 80 nm, and a ratio of particle size distribution d ₉₀ to the average particle size of 1.05 to 2.00. How to manufacture. The method of claim 1, wherein the particle size distribution d ₉₀ of the plate-like zinc oxide particles is 600 to 3000 nm. discharging the zinc-air battery to obtain an electrolyte containing an anionic zinc compound and zinc oxide;
diluting the electrolyte by adding a diluting solvent to the obtained electrolyte; and
A method for producing plate-like zinc oxide particles comprising the step of forming zinc oxide crystals by reacting a zinc salt with the diluted electrolyte solution,
The ratio of d _[4,3] , which is the average diameter calculated from the volume of the plate-like zinc oxide particles, to the average particle size of the plate-like zinc oxide particles (d _[4,3] / average particle size) is 0.3 to 2.0. A method of making zinc oxide particles.

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