CN113897194B - Light diffusion particle and preparation method and application thereof - Google Patents

Light diffusion particle and preparation method and application thereof Download PDF

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CN113897194B
CN113897194B CN202111088804.8A CN202111088804A CN113897194B CN 113897194 B CN113897194 B CN 113897194B CN 202111088804 A CN202111088804 A CN 202111088804A CN 113897194 B CN113897194 B CN 113897194B
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light diffusion
organic silicon
layer
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light
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CN113897194A (en
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罗培栋
颜妃妃
赵程
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Ningbo Dxc New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles

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Abstract

The invention relates to a light diffusion particle and a preparation method and application thereof. The light diffusion particle has a core-shell structure, wherein the core comprises an organic silicon microsphere and quantum dots coated on the surface of the organic silicon microsphere, the shell layer comprises an organic silicon layer, and the refractive index of the organic silicon microsphere is smaller than that of the organic silicon layer. The light diffusion film prepared by using the light diffusion particles as raw materials has excellent ultraviolet aging resistance, visible light transmittance and mechanical properties, and can well meet the performance requirements of equipment such as monitoring display devices and the like.

Description

Light diffusion particle and preparation method and application thereof
Technical Field
The invention relates to the technical field of light diffusion films, in particular to light diffusion particles and a preparation method and application thereof.
Background
A backlight system (BLU) mainly includes a light source, a light guide plate, a light diffusion film, a brightness enhancement film, a reflection film, and the like, and provides a light source for a Liquid Crystal Display (LCD) panel, which is a core of the LCD panel.
The light diffusion film in the BLU mainly functions to correct a diffusion angle and increase a light radiation area. However, the conventional light diffusion film has the problems of difficult ultraviolet aging resistance, low visible light transmittance and poor mechanical properties, and is difficult to meet the performance requirements of equipment such as monitoring display devices.
Disclosure of Invention
In view of the above, it is necessary to provide a light diffusion particle, a preparation method and an application thereof, in which the light diffusion particle is used as a raw material to prepare a light diffusion film having excellent ultraviolet aging resistance, visible light transmittance and mechanical properties, and capable of well meeting performance requirements of devices such as a monitoring display device.
The light diffusion particle is of a core-shell structure, wherein the core comprises an organic silicon microsphere and quantum dots coated on the surface of the organic silicon microsphere, the shell layer comprises an organic silicon layer, and the refractive index of the organic silicon microsphere is smaller than that of the organic silicon layer.
In one embodiment, the quantum dots have an average particle size of 3nm to 10nm, the quantum dots constitute a quantum dot layer, and the quantum dot layer has an average thickness of 5nm to 20nm.
In one embodiment, the material of the quantum dots comprises ZnS.
In one embodiment, the difference between the refractive index of the silicone layer and the refractive index of the silicone microspheres is greater than or equal to 0.07.
In one embodiment, the silicone microspheres have an average particle size of 3.5 μm to 9.5 μm;
and/or the average thickness of the organic silicon layer is 300nm-500nm.
The preparation method of the light diffusion particle is characterized by comprising the following steps:
providing organic silicon microspheres;
forming quantum dots on the surface of the organic silicon microsphere to obtain a core; and
and forming an organic silicon layer on the surface of the core to prepare the light diffusion particles, wherein the refractive index of the organic silicon microspheres is smaller than that of the organic silicon layer.
In one embodiment, the step of providing silicone microspheres comprises: adjusting the pH of an aqueous solution containing a first organic siloxane monomer to acidity, then adjusting the pH of the aqueous solution to alkalinity, and carrying out polycondensation reaction on the first organic siloxane monomer to obtain the organic silicon microspheres;
wherein the first organosiloxane monomer comprises at least one of methyltriethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, or n-hexyltrimethoxysilane.
In one embodiment, the step of forming quantum dots on the surface of the silicone microsphere to obtain a core comprises: mixing IIB group metal salt, sulfur salt and first suspension liquid containing organic silicon microspheres to obtain second suspension liquid, adjusting the pH value of the second suspension liquid to acidity, reacting the IIB group metal salt with the sulfur salt, and forming quantum dots on the surfaces of the organic silicon microspheres to obtain cores;
wherein the group IIB metal salt comprises zinc acetate, and the sulfur salt comprises Na 2 S or Na 2 S 2 O 3 At least one of the above, the molar ratio of the group IIB metal salt to the sulfur salt is 1:1 to 1:4, the aboveThe mass ratio of the IIB group metal salt to the organic silicon microspheres is 1:1-3:1.
In one embodiment, the step of forming a silicone layer on the surface of the core to obtain the light diffusion particle includes: mixing a second organic siloxane monomer and a third suspension liquid containing a core, and adjusting the pH of the fourth suspension liquid to be alkaline, wherein the second organic siloxane monomer forms an organic silicon layer on the surface of the core to prepare light diffusion particles;
the second organic siloxane monomer comprises at least one of phenyl trimethoxy silane, phenyl triethoxy silane, phenyl methyl dimethoxy silane, methyl phenyl diethoxy silane, diphenyl dimethoxy silane, p-aminophenyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-aminopropyl trimethoxy silane, N- (beta-aminoethyl) -3-aminopropyl methyl dimethoxy silane, vinyl trimethoxy silane or vinyl triethoxy silane, and the mass ratio of the second organic siloxane monomer to the organic silicon microsphere is 0.3:1-1:1.
A light diffusion film comprises the light diffusion particles.
In one embodiment, the light diffusion film comprises a substrate layer and a light diffusion layer, wherein the substrate layer and the light diffusion layer are stacked, and the light diffusion layer comprises the light diffusion particles.
In one embodiment, the mass fraction of the light diffusion particles in the light diffusion layer is 6% to 15%.
In an embodiment, the light diffusion film further comprises a scratch-resistant layer, the scratch-resistant layer is stacked on the surface of the substrate layer far away from the light diffusion layer, the scratch-resistant layer comprises scratch-resistant particles, at least one of the scratch-resistant particles is polyamide particles, polybutylmethacrylate particles or elastic silicone particles, the average particle size of the scratch-resistant particles is 100nm-500nm, and the mass fraction of the scratch-resistant particles in the scratch-resistant layer is 0.2% -0.5%.
In the light diffusion particles, quantum dots are arranged between the organic silicon microspheres and the organic silicon layer, and when the light diffusion film is prepared by taking the light diffusion particles as a raw material, firstly, the quantum dots have excellent scattering capacity and absorption capacity to ultraviolet rays, so that the light diffusion film has excellent ultraviolet ray aging resistance; secondly, the difference of the refractive indexes of the organic silicon layer and the organic silicon microspheres is cooperated with the fluorescence effect of the quantum dots, so that ultraviolet rays can be converted into visible light, and the light diffusion film is endowed with excellent visible light transmittance and light diffusion effect; thirdly, the quantum dots have excellent stability, so that the mechanical property of the light diffusion film can be improved; furthermore, the light diffusion film can well meet the performance requirements of equipment such as a monitoring display device and the like.
Drawings
FIG. 1 is a schematic structural diagram of a light diffusing particle according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a light diffusion film according to an embodiment of the present invention;
fig. 3 is a schematic structural view of a light diffusion film according to another embodiment of the present invention.
In the figure, 10, light diffusing particles; 101. organic silicon microspheres; 102. quantum dots; 103. a silicone layer; 20. a light diffusion layer; 30. a substrate layer; 40. a scratch-resistant layer; 50. and (4) scratch-resistant particles.
Detailed Description
The light diffusion particles provided by the present invention, and a method for preparing the same and applications thereof will be further described below.
As shown in fig. 1, the light diffusion particle 10 according to an embodiment of the present invention is mainly applied to a light diffusion film.
Specifically, the light diffusion particle 10 has a core-shell structure, wherein the core includes an organic silicon microsphere 101 and quantum dots 102 coated on the surface of the organic silicon microsphere 101, the shell includes an organic silicon layer 103, and the refractive index of the organic silicon microsphere 101 is smaller than that of the organic silicon layer 103.
In the light diffusion particle 10 of the present invention, the quantum dots 102 are disposed between the silicone microspheres 101 and the silicone layer 103, and the difference in refractive index between the silicone layer 103 and the silicone microspheres 101 is synergistic with the fluorescence effect of the quantum dots 102, so that ultraviolet light can be converted into visible light, thereby imparting excellent visible light transmittance and light diffusion effect to the light diffusion film.
In order to further improve the visible light transmittance of the light diffusion film and, at the same time, avoid agglomeration of the light diffusion particles 10 during the synthesis process, the average particle diameter of the light diffusion particles 10 is 4 μm to 10 μm, and more preferably 4 μm to 5 μm.
It is understood that the particle size of the light diffusion particle 10 provided by the present invention is composed of the particle size of the silicone microsphere 101, the particle size of the quantum dot 102 and the thickness of the silicone layer 103, and in an embodiment, the average particle size of the silicone microsphere 101 is 3.5 μm to 9.5 μm, and more preferably 3.5 μm to 4.5 μm.
In one embodiment, the refractive index of the silicone microspheres 101 is 1.40 to 1.45, and more preferably 1.41 to 1.43.
Since the quantum dot 102 is less stable in a high-humidity environment than the silicone layer 103, the silicone layer 103 covers the outer surface of the core to form a shell layer.
In one embodiment, the quantum dots 102 coated on the surface of the silicone microsphere 101 constitute a quantum dot layer. To prevent agglomeration of the quantum dots, it is preferable that the quantum dot layer is composed of continuous quantum dots 102.
It is understood that the quantum dots 102 refer to semiconductor nanoparticles having a particle size of 1nm to 20nm, in an embodiment, the quantum dots 102 refer to inorganic quantum dots, the material of the quantum dots 102 includes at least one of an oxide of a metal element in group IIB, a sulfide of a metal element in group IIB, a selenide of a metal element in group IIB, or a telluride of a metal element in group IIB, and specifically, the material of the quantum dots 102 includes at least one of CdO, cdS, cdSe, cdTe, znO, znS, znSe, znTe, hgO, hgS, hgSe, or HgTe, so as to reduce cytotoxicity of the quantum dots 102, and thus the material of the quantum dots 102 further preferably includes ZnS.
In the light diffusion particle 10 of the present invention, the quantum dot 102 has excellent scattering ability and absorption ability for ultraviolet rays, so that the light diffusion film has excellent ultraviolet ray aging resistance.
In order to further improve the ability of the light-diffusing particles 10 to absorb, scatter, and convert ultraviolet light into visible light, and at the same time, to avoid the quantum dots 102 from agglomerating during the formation of the quantum dot layer, in one embodiment, the average particle size of the quantum dots 102 is preferably 3nm to 10nm, and more preferably 4nm to 7nm; the quantum dot layer has an average thickness of 5nm to 20nm, more preferably 7nm to 15nm.
In one embodiment, the quantum dots 102 are spherical or spheroidal in shape.
In order to further improve the scattering ability of the light diffusion particles 10 and the ability to convert ultraviolet rays into visible light, in one embodiment, the difference between the refractive index of the silicone layer 103 and the refractive index of the silicone microspheres 101 is greater than or equal to 0.07, and more preferably greater than or equal to 0.1.
Considering that the silicone microspheres 101 are very prone to agglomeration during the process of coating the silicone layer, in one embodiment, the silicone layer 103 has an average thickness of 300nm to 500nm.
In addition, in the light diffusion particle 10 of the present invention, the quantum dot 102 has excellent stability, and further, the mechanical properties of the light diffusion film are improved.
The present invention provides a method for preparing light diffusion particles 10, comprising the steps of:
s1, providing an organic silicon microsphere 101;
s2, forming quantum dots 102 on the surface of the organic silicon microsphere 101 to obtain a core; and
and S3, forming an organic silicon layer 103 on the surface of the core to prepare the light diffusion particle 10, wherein the refractive index of the organic silicon microsphere 101 is smaller than that of the organic silicon layer 103.
In step S1, it should be noted that the source of the silicone microspheres 101 is not limited in the present invention, and the silicone microspheres 101 may be obtained by a purchased method or a self-prepared method, and when obtained by a self-prepared method, the method is not limited to a specific method.
In one embodiment, step S1 includes: the pH value of the aqueous solution containing the first organic siloxane monomer is adjusted to acidity and then adjusted to alkalinity, and the first organic siloxane monomer is subjected to polycondensation reaction to prepare the organic silicon microsphere 101.
In order to prevent the prepared silicone microspheres 101 from agglomerating, the aqueous solution containing the first organosiloxane monomer has a molar ratio of the first organosiloxane monomer to water of 1: 13 to 1: 30.
In order to better control the polycondensation process of the first organic siloxane monomer, in the step of adjusting the pH of the aqueous solution containing the first organic siloxane monomer to acidity and then to alkalinity, preferably, the pH of the solution containing the first organic siloxane monomer is adjusted to 4.0-6.0 by using the first acidic solution with the concentration of 0.01mol/L-0.02mol/L, then the temperature is raised to 30-40 ℃, the reaction is carried out for 1.5h-4.5h, the pH of the solution containing the first organic siloxane monomer is adjusted to 8.0-10.5 by using the first alkaline solution with the concentration of 0.01mol/L-0.02mol/L, and the reaction is continued for 2h-5h at 30-40 ℃; in one embodiment, the first acidic solution includes at least one of hydrochloric acid or sulfuric acid and the first basic solution includes ammonia.
In one embodiment, the first organosiloxane monomer comprises at least one of methyltriethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, or n-hexyltrimethoxysilane.
In one embodiment, step S2 includes: mixing IIB group metal salt, sulfur salt and the first suspension containing the organic silicon microspheres 101 to obtain a second suspension, adjusting the pH of the second suspension to acidity, reacting the IIB group metal salt with the sulfur salt, and forming quantum dots 102 on the surfaces of the organic silicon microspheres 101 to obtain cores.
The first suspension including the silicone microspheres 101 is a first reaction solution formed after the polycondensation reaction of the first organosiloxane monomer as described above, or is formed by mixing the silicone microspheres 101 obtained by a commercially available method with water.
In one embodiment, the group IIB metal salt comprises zinc acetate; the sulfur salt comprises Na 2 S or Na 2 S 2 O 3 At least one of (1).
In view of the yield of quantum dots and the size of the silicone microspheres 101, in one embodiment, the molar ratio of the first organosiloxane monomer to the group IIB metal salt is from 4: 1 to 30: 1, and more preferably from 10: 1 to 30: 1; the mass ratio of the IIB group metal salt to the organic silicon microsphere 101 is 1:1-3:1, more preferably 1.2: 1-2.9: 1, and still more preferably 1.8: 1-2.5: 1.
In order to control the size of ZnS quantum dots, the molar ratio of group IIB metal salt to sulfur salt is 1:1 to 1:4, more preferably 1:1 to 1: 3.
In order to better coat the quantum dots 102 on the surface of the silicone spheres 101, in the step of mixing the group IIB metal salt, the sulfur salt, and the first suspension including the silicone microspheres 101, it is preferable that the group IIB metal salt is first added to the first polar solvent, the sulfur salt is added to the second polar solvent, and the first polar solvent including the group IIB metal salt and the second polar solvent including the sulfur salt are mixed with the first suspension including the silicone microspheres 101. In one embodiment, the first polar solvent and the second polar solvent each include water and an alcohol solvent, the alcohol solvent includes one of ethanol, methanol or propanol, and the volume ratio of water to the alcohol solvent is 1: 1-10: 1, and more preferably 3: 1-5: 1.
In the step of adjusting the pH of the second suspension to acidity, in order to facilitate the adjustment of the pH, it is preferable to adjust the pH of the second suspension to 4.0 to 5.0 using a second acidic solution having a concentration of 0.1mol/L to 0.2 mol/L; in one embodiment, the second acidic solution includes at least one of acetic acid or formic acid.
In order to better prevent the quantum dots 102 from agglomerating in the process of forming the quantum dot layer, in the step of reacting the group IIB metal salt with the sulfur salt and forming the quantum dots 102 on the surface of the silicone microspheres 101, the reaction temperature is 50 ℃ to 80 ℃.
In one embodiment, in the step of reacting the group IIB metal salt with the sulfur salt and forming the quantum dots 102 on the surface of the silicone microsphere 101, the reaction time is 2.0h to 6.0h.
In one embodiment, step S3 comprises: the light diffusion particle 10 is prepared by mixing the second organosiloxane monomer and the third suspension including the core to obtain a fourth suspension, adjusting the pH of the fourth suspension to be alkaline, and forming the silicone layer 103 on the surface of the core by the second organosiloxane monomer.
The third suspension including the core is the second reaction solution obtained by reacting the group IIB metal salt with the sulfur salt as described above, or is formed by mixing the core prepared in step S2 with water.
In order to better prevent the quantum dots 102 from agglomerating, in one embodiment, an alcoholic solvent is further added in the step of mixing the second organosiloxane monomer and the third suspension including the core, wherein the alcoholic solvent includes one of ethanol, methanol or propanol, and the molar ratio of the second organosiloxane monomer to the alcoholic solvent is 1:1-1: 5.
In one embodiment, the second organosiloxane monomer comprises at least one of phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, p-aminophenyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -3-aminopropylmethyldimethoxysilane, vinyltrimethoxysilane, or vinyltriethoxysilane.
In the step of adjusting the pH of the fourth suspension to be alkaline, in order to facilitate the adjustment of the pH, it is preferable to adjust the pH of the fourth suspension to 8.0 to 10.5 using a second alkaline solution having a concentration of 0.01mol/L to 0.02mol/L, and in one embodiment, the second alkaline solution includes ammonia water.
In one embodiment, the temperature is 20 ℃ to 45 ℃ in the step of forming the silicone layer 103 on the surface of the core with the second organosiloxane monomer.
In one embodiment, the reaction time in the step of forming the silicone layer 103 of the second organosiloxane monomer at the surface of the core is from 1.0h to 4.0h.
The preparation method provided by the invention realizes simple preparation of the light diffusion particles 10 and is suitable for industrial production.
The present invention provides a light diffusion film comprising the above light diffusion particles 10.
As shown in fig. 2, the light diffusion film according to an embodiment of the present invention includes a substrate layer 30 and a light diffusion layer 20, which are stacked, and the light diffusion layer 20 includes the light diffusion particles 10.
In one embodiment, the material of the substrate layer 30 includes polyethylene terephthalate; the thickness of the base material layer 30 is 50 μm to 250 μm, and more preferably 50 μm to 188 μm.
In order to optimize the overall performance of the light diffusion film to be produced, in one embodiment, the mass fraction of the light diffusion particles 10 in the light diffusion layer 20 is 6% to 15%, and more preferably 10% to 13%.
In one embodiment, the base material of the light diffusion layer 20 is formed by heat or ultraviolet curing a resin composition; the thickness of the light diffusion layer 20 is 8 μm to 13 μm, and more preferably 10 μm to 12 μm.
In one embodiment, the resin composition includes 10 to 25 parts by mass of an acrylate monomer, 25 to 50 parts by mass of an oligomer, and 0.25 to 0.50 parts by mass of a photoinitiator.
In one embodiment, the acrylate monomer includes at least one of 2-phenoxyethyl acrylate, o-phenylphenoxyethyl acrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, pentaerythritol triacrylate, or trimethylolpropane triacrylate.
The oligomer can improve the film forming properties of the resin composition, and in one embodiment, the oligomer is one of epoxy acrylates, urethane acrylates, or polyester acrylates.
In one embodiment, the photoinitiator includes at least one of photoinitiator 907, photoinitiator 1490, or photoinitiator 184.
As shown in fig. 3, in the light diffusion film according to another embodiment of the present invention, in order to prevent the light diffusion film from being scratched, the light diffusion film further includes a scratch-resistant layer 40, and the scratch-resistant layer 40 is stacked on the surface of the substrate layer 30 away from the light diffusion layer 20.
In one embodiment, the scratch resistant layer 40 is formed by heat or ultraviolet curing the resin composition, and the thickness of the scratch resistant layer 40 is 5 μm to 7 μm. Note that, the selection of the resin composition in the scratch-resistant layer 40 is referred to the light diffusion layer 20.
In one embodiment, the scratch-resistant layer 40 comprises scratch-resistant particles 50, the average particle size of the scratch-resistant particles 50 is 100nm to 500nm, and the mass fraction of the scratch-resistant particles in the scratch-resistant layer 40 is 0.2% to 0.5%.
In one embodiment, the scratch resistant particles 50 are one of Polyamide (PA) particles, polybutylmethacrylate (PBMA) particles, or elastomeric silicone particles.
The light diffusion film provided by the invention has excellent ultraviolet aging resistance, visible light transmittance, light diffusion effect and mechanical property, and can well meet the performance requirements of equipment such as a monitoring display device and the like.
Hereinafter, the light diffusion particle, the method for preparing the same and the application thereof will be further described by the following specific examples.
Example 1
Mixing 0.05mol of methyltriethoxysilane and 1.2mol of distilled water, stirring for 30min, adjusting the pH of a solution containing the methyltriethoxysilane to 4.0 by using 0.02mol/L hydrochloric acid, heating to 35 ℃, reacting for 4h, adjusting the pH to 10 by using 0.02mol/L ammonia water, and continuously reacting for 4.5h at 35 ℃ to perform polycondensation reaction on the methyltriethoxysilane to form a first suspension containing the organic silicon microspheres 101.
5mL of 1mol/L zinc acetate solution and 5mL of 1mol/L Na are sequentially added into the first suspension dropwise 2 The S solution is used to obtain a second suspension, a zinc acetate solution and Na 2 The solvent of the S solution is a mixed solvent of water and ethanol, the volume ratio of the water to the ethanol is 3:1, the pH of the second suspension is adjusted to 4.0 by 0.15mol/L acetic acid after the uniform mixing, the temperature is raised to 45 ℃ for reaction for 4.0h, and the zinc acetate and Na 2 S forming ZnS quantum dots 102 on the surface of the organic silicon microsphere 101, wherein the ZnS quantum dots 102 form a quantum dot layer, and a third suspension containing a core is obtained.
Adding 0.025mol of phenyltriethoxysilane and 0.125mol of ethanol into the third suspension, uniformly mixing to obtain a fourth suspension, adjusting the pH value of the fourth suspension to 10 by using 0.02mol/L ammonia water, reacting for 3 hours at 40 ℃, performing polycondensation reaction on the phenyltriethoxysilane to form an organic silicon layer 103 on the surface of the core, cooling to room temperature, performing suction filtration, sequentially washing with distilled water and ethanol, filtering, and performing vacuum drying on the washed filter cake for 6 hours at 80 ℃ to obtain the light diffusion particles 10.
The transmission electron microscope detection shows that the average grain diameter of the light diffusion particles 10 is 4.1 μm, wherein the average grain diameter of the organic silicon microsphere 101 is 3.8 μm, the average thickness of the quantum dot layer is 8.3nm, the average grain diameter of the quantum dots 102 is 4.5nm, and the thickness of the organic silicon layer 103 is 0.3 μm.
The refractive index of the organic silicon microsphere 101 is 1.43 and the refractive index of the organic silicon layer 103 is 1.57 detected by an Abbe refractometer.
Example 2
Mixing 0.05mol of methyltriethoxysilane and 1.2mol of distilled water, stirring for 30min, adjusting the pH of a solution containing the methyltriethoxysilane to 4.0 by using 0.02mol/L hydrochloric acid, reacting at 25 ℃ for 2.5h, adjusting the pH to 10 by using 0.02mol/L ammonia water, and continuing to react at 40 ℃ for 4.5h to perform polycondensation reaction on the methyltriethoxysilane to form a first suspension containing the organic silicon microspheres 101.
5mL of a 1mol/L zinc acetate solution and 5mL of 1mol/L Na are sequentially added dropwise to the first suspension 2 S 2 O 3 The solution is obtained as a second suspension, zinc acetate solution, na 2 S 2 O 3 The solvent of the solution is a mixed solvent of water and ethanol, the volume ratio of the water to the ethanol is 3:1, the pH of the second suspension is adjusted to 4.0 by 0.15mol/L acetic acid after the mixture is uniformly mixed, the temperature is raised to 70 ℃ for reaction for 4.0h, and zinc acetate and Na 2 S 2 O 3 ZnS quantum dots 102 are formed on the surface of the organic silicon microsphere 101, and the ZnS quantum dots 102 form a quantum dot layer to obtain a third suspension liquid containing a core.
Adding 0.025mol of phenyltriethoxysilane and 0.125mol of ethanol into the third suspension, uniformly mixing to obtain a fourth suspension, adjusting the pH value of the fourth suspension to 10 by using 0.02mol/L ammonia water, reacting for 1h at 40 ℃, performing polycondensation reaction on the phenyltriethoxysilane to form an organic silicon layer 103 on the surface of the core, cooling to room temperature, performing suction filtration, sequentially washing with distilled water and ethanol, filtering, and performing vacuum drying on the washed filter cake for 6h at 80 ℃ to obtain the light diffusion particles 10.
The transmission electron microscope detection shows that the average grain diameter of the light diffusion particles 10 is 4.6 μm, wherein the average grain diameter of the organic silicon microsphere 101 is 4.3 μm, the average thickness of the quantum dot layer is 11.1nm, the average grain diameter of the quantum dots 102 is 6.8nm, and the thickness of the organic silicon layer 103 is 0.30 μm.
The refractive index of the organic silicon microsphere 101 is 1.43 and the refractive index of the organic silicon layer 103 is 1.57 detected by an Abbe refractometer.
Example 3
Mixing 0.05mol of methyltriethoxysilane and 1.2mol of distilled water, stirring for 30min, adjusting the pH of a solution containing the methyltriethoxysilane to 4.0 by using 0.02mol/L hydrochloric acid, heating to 40 ℃, reacting for 3h, adjusting the pH to 10 by using 0.02mol/L ammonia water, and continuously reacting for 2h at 40 ℃ to perform polycondensation reaction on the methyltriethoxysilane to form a first suspension containing the organic silicon microspheres 101.
2mL of 1mol/L zinc acetate solution and 8mL of 1mol/L Na are sequentially added dropwise to the first suspension 2 The S solution is used to obtain a second suspension, a zinc acetate solution and Na 2 The solvent of the S solution is a mixed solvent of water and ethanol, the volume ratio of the water to the ethanol is 3:1, the pH of the second suspension is adjusted to 4.0 by 0.15mol/L acetic acid after the mixture is uniformly mixed, the temperature is raised to 50 ℃ for reaction for 4.0h, and zinc acetate and Na 2 S forms ZnS quantum dots 102 on the surface of the organic silicon microsphere 101, and the ZnS quantum dots 102 form a quantum dot layer to obtain a third suspension liquid including a core.
Adding 0.025mol of phenylmethyldimethoxysilane and 0.125mol of ethanol into the third suspension, uniformly mixing to obtain a fourth suspension, adjusting the pH value of the fourth suspension to 10 by using 0.02mol/L ammonia water, reacting for 3 hours at 40 ℃, performing polycondensation reaction on the phenyltriethoxysilane to form an organic silicon layer 103 on the surface of a core, cooling to room temperature, performing suction filtration, sequentially washing with distilled water and ethanol, filtering, and performing vacuum drying on a washed filter cake for 6 hours at 80 ℃ to obtain the light diffusion particles 10.
The transmission electron microscope detects that the average grain diameter of the light diffusion particle 10 is 4.5 μm, wherein the average grain diameter of the organic silicon microsphere 101 is 4.0 μm, the average thickness of the quantum dot layer is 5.1nm, the average grain diameter of the quantum dot 102 is 3.1nm, and the thickness of the organic silicon layer 103 is 0.48 μm.
The refractive index of the organic silicon microsphere 101 is 1.43 and the refractive index of the organic silicon layer 103 is 1.56 through Abbe refractometer detection.
Example 4
Mixing 0.06mol of methyltriethoxysilane and 1.8mol of distilled water, stirring for 30min, adjusting the pH of a solution containing the methyltriethoxysilane to 4.0 by using 0.02mol/L hydrochloric acid, heating to 40 ℃, reacting for 4h, adjusting the pH to 10 by using 0.02mol/L ammonia water, and continuously reacting for 4.5h at 40 ℃ to perform polycondensation reaction on the methyltriethoxysilane to form a first suspension containing the organic silicon microspheres 101.
2mL of 1mol/L zinc acetate solution and 8mL of 1mol/L Na are sequentially added dropwise to the first suspension 2 The S solution is used to obtain a second suspension, a zinc acetate solution and Na 2 The solvent of the S solution is a mixed solvent of water and ethanol, the volume ratio of the water to the ethanol is 3:1, the pH of the second suspension is adjusted to 4.0 by 0.15mol/L acetic acid after the mixture is uniformly mixed, the temperature is raised to 60 ℃ for reaction for 3.0h, and zinc acetate and Na 2 S forming ZnS quantum dots 102 on the surface of the organic silicon microsphere 101, wherein the ZnS quantum dots 102 form a quantum dot layer to obtain a third suspension liquid containing a core.
Adding 0.025mol of methyl phenyl diethoxy silane and 0.125mol of ethanol into the third suspension, uniformly mixing to obtain a fourth suspension, adjusting the pH value of the fourth suspension to 10 by using 0.02mol/L ammonia water, reacting for 3 hours at 40 ℃, performing polycondensation reaction on the methyl phenyl diethoxy silane to form an organic silicon layer 103 on the surface of a core, cooling to room temperature, performing suction filtration, sequentially washing with distilled water and ethanol, filtering, and performing vacuum drying on a washed filter cake for 6 hours at 80 ℃ to obtain the light diffusion particles 10.
The transmission electron microscope detects that the average grain diameter of the light diffusion particle 10 is 4.1 μm, wherein the average grain diameter of the organic silicon microsphere 101 is 3.6 μm, the average thickness of the quantum dot layer is 6.8nm, the average grain diameter of the quantum dot 102 is 3.7nm, and the thickness of the organic silicon layer 103 is 0.46 μm.
The refractive index of the organic silicon microsphere 101 is 1.43 and the refractive index of the organic silicon layer 103 is 1.54 through Abbe refractometer detection.
Example 5
The light diffusion film of the present embodiment includes a scratch-resistant layer 40, a base material layer 30, and a light diffusion layer 20, which are sequentially laminated. Wherein, the thickness of the scratch-resistant layer 40 is 5 μm, the scratch-resistant layer is formed by processing the resin composition in an ultraviolet curing mode, the scratch-resistant layer 40 also comprises PA particles, the average particle size of the PA particles is 100nm, and the mass fraction of the PA particles in the scratch-resistant layer 40 is 0.3%; the thickness of the substrate layer 30 is 50 μm, and the material of the substrate layer 30 is PET; the light diffusion layer 20 had a thickness of 10 μm and was formed by ultraviolet curing of the resin composition, and the light diffusion layer 20 further included uniformly dispersed light diffusion particles 10 prepared in example 1, and the mass fraction of the light diffusion particles 10 in the light diffusion layer 20 was 6%.
The resin composition includes 20 parts by mass of 2-phenoxyethyl acrylate, 45 parts by mass of urethane acrylate, and 0.35 part by mass of a photoinitiator 907.
Example 6
A light diffusion film was prepared with reference to example 5, except that the light diffusion particles 10 prepared in example 1 were replaced with the light diffusion particles 10 prepared in example 2.
Example 7
A light diffusion film was prepared with reference to example 5, except that the light diffusion particles 10 prepared in example 1 were replaced with the light diffusion particles 10 prepared in example 3.
Example 8
A light diffusion film was prepared with reference to example 5, except that the light diffusion particles 10 prepared in example 1 were replaced with the light diffusion particles 10 prepared in example 4.
Example 9
A light diffusion film was prepared with reference to example 6, except that the mass fraction of PA particles in the scratch-resistant layer 40 was 0.5%; the mass fraction of the light diffusion particles 10 in the light diffusion layer 20 is 10%; the resin composition included 25 parts by mass of 1, 6-hexanediol diacrylate, 30 parts by mass of epoxy acrylate, and 0.20 part by mass of a photoinitiator 1490.
Example 10
A light diffusion film was prepared with reference to example 7, except that the mass fraction of PA particles in the scratch-resistant layer 40 was 0.2%; the mass fraction of the light diffusion particles 10 in the light diffusion layer 20 is 10%; the resin composition includes 25 parts by mass of dipropylene glycol diacrylate, 50 parts by mass of urethane acrylate, and 0.5 part by mass of a photoinitiator 1490.
Example 11
A light diffusion film was prepared with reference to example 8, except that the mass fraction of the light diffusion particles 10 in the light diffusion layer 20 was 10%; the resin composition includes 18 parts by mass of pentaerythritol triacrylate, 45 parts by mass of epoxy acrylate, and 0.35 parts by mass of a photoinitiator 184.
Comparative example 1
A light diffusion film was prepared with reference to example 11, except that the light diffusion particles 10 did not have a quantum dot layer. Through the detection of a transmission electron microscope,
the light-diffusing particles 10 had an average particle diameter of 4.06. Mu.m, wherein the silicone microspheres 101 had an average particle diameter of 3.6. Mu.m, and the silicone layer 103 had a thickness of 0.46. Mu.m. The refractive index of the organic silicon microsphere 101 is 1.43 and the refractive index of the organic silicon layer 103 is 1.54 through Abbe refractometer detection.
Comparative example 2
A light diffusion film was prepared with reference to example 11, except that the light diffusion particles 10 did not have the silicone layer 103. The transmission electron microscope detection shows that the average grain diameter of the light diffusion particles 10 is 3.61 microns, wherein the average grain diameter of the organic silicon 9.0 microspheres 101 is 3.6 microns, the thickness of the quantum dot layer is 6.8nm, and the average grain diameter of the quantum dots 102 is 3.7nm. The refractive index of the organic silicon microsphere 101 is 1.43 detected by an Abbe refractometer.
Comparative example 3
A light diffusion film was produced with reference to comparative example 1, except that ZnS quantum dots 102 were further included in the light diffusion film, the average particle diameter of the ZnS quantum dots 102 was 3.7nm, and the mass fraction in the light diffusion film was 1%.
Test example
The optical properties of the light diffusion films obtained in examples 5 to 11 and comparative examples 1 to 3 were measured according to GB/T2410-2008, and the results are shown in Table 1.
Mechanical property tests were performed on the light diffusion films prepared in examples 5 to 11 and comparative examples 1 to 3 according to GB/T13542.2 to 2009, and specific test results are shown in table 2.
The light diffusion films obtained in examples 5 to 11 and comparative examples 1 to 3 were subjected to an aging resistance test, and the first yellowness index: the treatment conditions of the light diffusion film were 90 ℃ and 90% RH treatment for 400h, second yellowness index: the light diffusion film is processed at 90 deg.C, 395nm,1.5W/m 2 The treatment time is 400h, and the specific test results are shown in Table 2.
TABLE 1
Figure BDA0003266506640000171
TABLE 2
Figure BDA0003266506640000172
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.

Claims (13)

1. The light diffusion particle is characterized in that the light diffusion particle has a core-shell structure, wherein a core comprises an organic silicon microsphere and quantum dots coated on the surface of the organic silicon microsphere, the material of the quantum dots comprises at least one of oxides, sulfides, selenides or tellurides of group IIB metal elements, and the shell comprises an organic silicon layer, and the refractive index of the organic silicon microsphere is smaller than that of the organic silicon layer.
2. The light-diffusing particle according to claim 1, wherein the quantum dot has an average particle diameter of 3nm to 10nm, and the quantum dot constitutes a quantum dot layer having an average thickness of 5nm to 20nm.
3. The light-diffusing particle according to claim 1, wherein the material of said quantum dot comprises ZnS.
4. The light-diffusing particle according to any one of claims 1 to 3, wherein the difference between the refractive index of the silicone layer and the refractive index of the silicone microsphere is 0.07 or more.
5. The light-diffusing particle according to any one of claims 1 to 3, wherein the silicone microsphere has an average particle diameter of 3.5 μm to 9.5 μm;
and/or the average thickness of the organic silicon layer is 300nm-500nm.
6. A method for producing the light-diffusing particle according to any one of claims 1 to 5, comprising the steps of:
providing organic silicon microspheres;
forming quantum dots on the surface of the organic silicon microsphere to obtain a core; and
and forming an organic silicon layer on the surface of the core to prepare the light diffusion particles, wherein the refractive index of the organic silicon microspheres is smaller than that of the organic silicon layer.
7. The method of producing the light-diffusing particle according to claim 6, wherein the step of providing the silicone microsphere includes: adjusting the pH of an aqueous solution containing a first organic siloxane monomer to acidity, then adjusting the pH to alkalinity, and carrying out polycondensation reaction on the first organic siloxane monomer to obtain the organic silicon microspheres;
wherein the first organosiloxane monomer comprises at least one of methyltriethoxysilane, methyltrimethoxysilane, propyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, or n-hexyltrimethoxysilane.
8. The method of claim 6, wherein the step of forming quantum dots on the surface of the silicone microsphere to obtain a core comprises: mixing IIB group metal salt, sulfur salt and first suspension liquid containing organic silicon microspheres to obtain second suspension liquid, adjusting the pH value of the second suspension liquid to acidity, reacting the IIB group metal salt with the sulfur salt, and forming quantum dots on the surfaces of the organic silicon microspheres to obtain cores;
wherein the group IIB metal salt comprises zinc acetate and the sulfur salt comprises Na 2 S or Na 2 S 2 O 3 The molar ratio of the group IIB metal salt to the sulfur salt is 1.
9. The method of claim 6, wherein the step of forming a silicone layer on the surface of the core to form the light-diffusing particle comprises: mixing a second organic siloxane monomer and a third suspension containing a core to obtain a fourth suspension, adjusting the pH of the fourth suspension to be alkaline, and forming an organic silicon layer on the surface of the core by using the second organic siloxane monomer to prepare light diffusion particles;
wherein the second organic siloxane monomer comprises at least one of phenyl trimethoxy silane, phenyl triethoxy silane, phenyl methyl dimethoxy silane, methyl phenyl diethoxy silane, diphenyl dimethoxy silane, p-aminophenyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-aminopropyl trimethoxy silane, N- (beta-aminoethyl) -3-aminopropyl methyl dimethoxy silane, vinyl trimethoxy silane or vinyl triethoxy silane, and the mass ratio of the second organic siloxane monomer to the organic silicon microsphere is 0.3.
10. A light diffusing film comprising the light diffusing particles according to any one of claims 1 to 5.
11. The light diffusion film according to claim 10, comprising a base material layer and a light diffusion layer which are laminated, wherein the light diffusion layer comprises the light diffusion particles according to any one of claims 1 to 5.
12. The light diffusion film according to claim 11, wherein a mass fraction of the light diffusion particles in the light diffusion layer is 6% to 15%.
13. The light diffusion film according to claim 11, further comprising a scratch-resistant layer laminated on a surface of the base material layer away from the light diffusion layer, wherein the scratch-resistant layer comprises scratch-resistant particles, the scratch-resistant particles comprise at least one of polyamide particles, polybutylmethacrylate particles, or elastic silicone particles, the average particle size of the scratch-resistant particles is 100nm to 500nm, and the mass fraction of the scratch-resistant particles in the scratch-resistant layer is 0.2% to 0.5%.
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