Optical resin composition and preparation method and application thereof
阅读说明：本技术 一种光学树脂组合物及其制备方法和应用 (Optical resin composition and preparation method and application thereof ) 是由 邹菁 江吉周 王海涛 于 2021-08-11 设计创作，主要内容包括：本发明公开了一种光学树脂组合物及其制备方法和应用,组成按重量份数计如下：20-40重量份的无机纳米颗粒,5-15重量份的环氧丙烯酸类单体或其寡聚物,5-10重量份的光引发剂,20-60重量份的溶剂；本发明制备得到了环境友好型且对显示装置影响较小的高折射率光学材料,将其单独或与低折射率材料共同制作微透镜阵列微结构应用至OLED等显示终端应用的封装层上,制备的显示装置出光效率提高20％以上,是一种优异的显示装置光学树脂组合物,在OLED器件,Mini LED,Micro LED等方面具有广阔的应用前景。(The invention discloses an optical resin composition, a preparation method and an application thereof, wherein the optical resin composition comprises the following components in parts by weight: 20-40 parts of inorganic nanoparticles, 5-15 parts of epoxy acrylic monomers or oligomers thereof, 5-10 parts of photoinitiator and 20-60 parts of solvent; the high-refractive-index optical material which is environment-friendly and has small influence on the display device is prepared, the Micro-lens array microstructure is prepared from the high-refractive-index optical material alone or together with the low-refractive-index material and applied to the packaging layer of the OLED and other display terminals, the light-emitting efficiency of the prepared display device is improved by more than 20%, and the prepared display device is an excellent optical resin composition for the display device and has wide application prospects in the aspects of OLED devices, Mini LEDs, Micro LEDs and the like.)
1. An optical resin composition is characterized by comprising the following components in parts by weight:
20-40 parts of inorganic nanoparticles, 5-15 parts of epoxy acrylic monomers or oligomers thereof, 5-10 parts of photoinitiator and 20-60 parts of solvent;
wherein the structural general formula of the epoxy acrylic monomer is as follows:
wherein R1 and R2 are respectively and independently selected from: hydrogen, alkyl with carbon chain length of 1-6, phenyl unsubstituted or substituted by cyano, nitro, fluoro, alkyl with carbon chain length of 1-6; ar is selected from: an alkyl group having a carbon chain length of 2 to 12 which is unsubstituted or substituted with a hydroxyl group or a fluorine group, an ether group having a carbon chain length of 2 to 12 which is unsubstituted or substituted with a hydroxyl group or a fluorine group, or an aromatic ring compound having a carbon chain length of 2 to 12 which is unsubstituted or substituted with a hydroxyl group, a fluorine group, a cyano group, a nitro group, or an alkyl group having a carbon chain length of 1 to 6; n is a natural number from 1 to 8.
2. The optical resin composition according to claim 1, wherein the alkyl group having a carbon chain length of 1 to 6 is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl;
the alkane with the carbon chain length of 2-12 is selected from one of the following structures:
the ether group with the carbon chain length of 2-12 is selected from one of the following structures:
the aromatic ring compound with the carbon chain length of 2-12 is selected from one of the following structures:
wherein, is a site bridging with the epoxyacrylic functional group.
3. The optical resin composition according to claim 1, wherein the inorganic nanoparticles are fine metal oxide particles or fine metal sulfide particles having a refractive index of 2 or more in a visible light region, and the particle diameter of the nanoparticles is 5 to 10 nm.
4. The optical resin composition according to claim 3, wherein the inorganic nanoparticles comprise 1 to 2 metal elements selected from the group consisting of zirconium (Zr), titanium (Ti), zinc (Zn), germanium (Ge), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), antimony (Sb), cerium (Ce), neodymium (Nd), hafnium (Hf), tantalum (Ta) and bismuth (Bi).
5. The optical resin composition according to claim 1, wherein the epoxy acrylic monomer is selected from one of the following structural formulas:
6. the optical resin composition as defined in claim 1, wherein the photoinitiator is one of α -hydroxy ketone photoinitiator, benzoin compound, acylphosphine oxide photoinitiator, acetophenone photoinitiator, and morpholinoketone photoinitiator.
7. The optical resin composition according to claim 1, wherein the solvent is one or any mixture of lipids, alcohols, ethers, ketones, and aromatics.
8. The optical resin composition according to claim 1, wherein a functional assistant is further added to the optical resin composition; the functional auxiliary agent is one or more of a surfactant, a flatting agent, a coupling agent, a defoaming agent and a polymerization inhibitor; the addition amount of each functional auxiliary agent is 5-15 parts by weight.
9. A method for producing an optical resin composition as claimed in any one of claims 1 to 8, characterized by comprising the steps of:
adding 20-60 parts by weight of solvent into a reaction vessel, then adding 5-15 parts by weight of epoxy acrylic monomer or oligomer thereof heated to more than 60 ℃ and 5-10 parts by weight of photoinitiator, fully and uniformly stirring, then adding 20-40 parts by weight of inorganic nano particles, and continuously and uniformly stirring and mixing at normal temperature to obtain the optical resin composition.
10. Use of the optical resin composition according to any one of claims 1 to 8 in the encapsulation of OLED, Mini LED, Micro LED displays, characterized in that the optical resin composition is cured to form a film by coating, spraying or ink-jet printing under the action of heat or uv light, and the obtained film has a high refractive index (1.6 < n < 1.8) and forms a microlens array with a low refractive index material (n-1.5).
Technical Field
The invention belongs to the technical field of photoelectric material application, and particularly relates to an optical resin composition and a preparation method and application thereof.
Background
The OLED display technology is called Organic Light Emitting Diode display, has the advantages of thin thickness, low power consumption, and being foldable, and is called as "illusion display technology". In mobile display products (such as mobile phones and watches), the market share of OLED displays (57%) has exceeded LCD technology (43%), becoming mainstream display technology; and gradually permeate into the fields of notebook computers (Laptop), PC monitors and TVs. Through reasonable molecular design and device optimization, the internal quantum efficiency of the OLED light-emitting device can reach 100%. Due to the difference in refractive index between the interface between the electrode film and the glass substrate and between the glass substrate and the air, at a certain viewing angle (θ), the light is totally reflected at the interface, which means that the light exceeding the θ angle cannot exit to the outside of the display and is lost. Studies have shown that the light emitted to the space outside the device accounts for about 20% of the total amount of light emitted from the organic material thin film, and the remaining about 80% of the light is confined mainly in the form of guided waves in the organic material thin film, the transparent electrode, and the glass substrate. The low luminous efficiency increases the power consumption of the OLED display, reduces the endurance time of the watch/mobile phone, and becomes a pain point for consumers to use OLED display products.
At present, there are three types of methods for improving the light extraction efficiency of OLEDs: and forming folds, photonic crystals, micro-lens arrays and the like on the light-emitting surface of the substrate. The first two schemes are unstable in process and uncontrollable in production, and the adoption of the technology for manufacturing the microlens array is considered to be the most reliable technology for improving the light extraction efficiency, and is adopted by various large panel factories at home and abroad. The current OLED display has low production yield due to a complicated production process. Microlens arrays are a new technology that needs to ensure efficient film formation of high refractive materials while minimizing damage to the OLED display. Therefore, in order to overcome the defects of the microlens array technology, it is necessary to develop a material that is low in cost, high in efficiency, simple in process, and capable of being printed by ink jet, so that the light extraction rate is improved, meanwhile, the damage to the OLED display is reduced, and the production yield is improved.
Disclosure of Invention
The invention mainly aims to provide an optical resin composition, a preparation method and application thereof, the optical resin composition can remarkably improve the light-emitting efficiency of OLED display devices, Mini LEDs, Micro LEDs and other display devices, can be prepared into a film by using a cold process with small influence on the display devices such as ink-jet printing, silk-screen printing and the like, and is an excellent optical material for the display devices.
In order to achieve the purpose, the technical scheme is as follows:
an optical resin composition comprises 20-40 parts by weight of inorganic nanoparticles, 5-15 parts by weight of epoxy acrylic monomers or oligomers thereof, 5-10 parts by weight of photoinitiator and 20-60 parts by weight of solvent;
wherein the structural general formula of the epoxy acrylic monomer is as follows:
wherein R1 and R2 are respectively and independently selected from: hydrogen, alkyl with carbon chain length of 1-6, phenyl unsubstituted or substituted by cyano, nitro, fluoro, alkyl with carbon chain length of 1-6; ar is selected from: an alkyl group having a carbon chain length of 2 to 12 which is unsubstituted or substituted with a hydroxyl group or a fluorine group, an ether group having a carbon chain length of 2 to 12 which is unsubstituted or substituted with a hydroxyl group or a fluorine group, or an aromatic ring compound having a carbon chain length of 2 to 12 which is unsubstituted or substituted with a hydroxyl group, a fluorine group, a cyano group, a nitro group, or an alkyl group having a carbon chain length of 1 to 6; n is a natural number from 1 to 8.
According to the scheme, the alkyl with the carbon chain length of 1-6 is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and n-pentyl;
the alkane with the carbon chain length of 2-12 is selected from one of the following structures:
the ether group with the carbon chain length of 2-12 is selected from one of the following structures:
the aromatic ring compound with the carbon chain length of 2-12 is selected from one of the following structures:
wherein, is a site bridging with the epoxyacrylic functional group.
According to the scheme, the inorganic nanoparticles are metal oxide particles or metal sulfide particles with the refractive index of more than 2 in a visible light region (380-780 nm), and the particle size of the nanoparticles is 5-10 nm.
According to the scheme, the inorganic nano-particles contain 1-2 metal elements of zirconium (Zr), titanium (Ti), zinc (Zn), germanium (Ge), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), antimony (Sb), cerium (Ce), neodymium (Nd), hafnium (Hf), tantalum (Ta) and bismuth (Bi).
According to the scheme, the epoxy acrylic monomer is selected from one of the following structural formulas:
according to the scheme, the photoinitiator is one of an alpha-hydroxy ketone photoinitiator, a benzoin compound, an acyl phosphine oxide photoinitiator, an acetophenone photoinitiator and a morpholinone photoinitiator.
The benzoin compound is selected from: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin dimethyl ether, and benzoin diethyl ether; the acylphosphine oxide photoinitiator is selected from: (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, ethyl (2,4, 6-trimethylbenzoyl) phenylphosphonate; the acetophenone photoinitiator is selected from: 2, 2-dimethoxyacetophenone, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone; the alpha-hydroxy ketone photoinitiator is selected from: 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-2-methyl-1- [4- (tert-butyl) phenyl ] -1-propanone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-hydroxyethoxy) phenyl-1-propanone, poly [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone ], bifunctional alpha-hydroxyketone; the morpholinoketone photoinitiator is selected from: 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone.
According to the scheme, the solvent is one or any mixture of lipids, alcohols, ethers, ketones and aromatics.
The ester solvent is selected from: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxyamyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethylene glycol diacetate, 1, 3-butanediol diacetate, 1, 6-hexanol diacetate, cyclohexanol acetate; the alcohols are selected from: cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol; the ethers are selected from: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; the ketones are selected from: acetone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone; the benzene is selected from: toluene, xylene.
According to the scheme, the optical resin composition also contains a functional auxiliary agent; the functional auxiliary agent is one or more of a surfactant, a flatting agent, a coupling agent, a defoaming agent and a polymerization inhibitor; the addition amount of each functional auxiliary agent is 5-15 parts by weight.
The surfactant is selected from: a fluorine-based surfactant or a silicone-based surfactant; fluorine-based surfactants include, for example, 1,1,2, 2-tetrafluorooctyl (1,1,2, 2-tetrafluoropropyl) ether, 1,1,2, 2-tetrafluorooctylhexyl ether, hexaethylene glycol (1,1,2,2,3, 3-hexafluoropentyl) ether, octaethylene glycol bis (1,1,2, 2-tetrafluorobutyl) ether, octapropylene glycol bis (1,1,2, 2-tetrafluorobutyl) ether, hexapropylene glycol bis (1,1,2,2,3, 3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, N- [3- (perfluorooctanesulfonamide) propyl ] -N, N' -dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salt, perfluoroalkyl-N-ethylsulfonylglycinate salt, etc., the silicone surfactant may be exemplified by those available under the trade name of Tollissilicon corporation: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190, and trade name KP341 manufactured by shin-Etsu chemical industries, Inc.
The defoaming agent is selected from: silicone defoaming agents, mineral oil defoaming agents, polyether-modified silicone defoaming agents, which may be exemplified include polydimethylsiloxane, methylphenylpolysiloxane, or methylvinylpolysiloxane, or BYK-141, BYK-A530, BYK-A555, BYK-024, BYK-028, BYK-052, BYK-054, BYK-055, BYK-057, BYK-065, BYK-066N, BYK-088, which are trade names manufactured by Bik chemical company, Germany.
The leveling agent is selected from an organic silicon leveling agent, a modified silane leveling agent or a non-silane leveling agent, the organic silicon leveling agent is preferably polydimethylsiloxane, polydiphenylsiloxane or polymethylphenyl polysiloxane, the modified silane leveling agent is preferably polyether modified polydimethylsiloxane, polyester modified polydimethylsiloxane or polyether modified polyorganosiloxane, and the non-silane leveling agent is preferably polyacrylate leveling agent.
The coupling agent is selected from: the silane coupling agent is preferably a trifunctional organosilane, a tetrafunctional organosilane or a silicate compound, and examples of the trifunctional organosilane include: methyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 4-styryltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 3-trimethoxysilylpropylsuccinic anhydride, 3,3, 3-trifluoropropyltrimethoxysilane, 3- [ (3-ethyl-3-oxetanyl) methoxy ] propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (4-aminophenyl) propyltrimethoxysilane, 1- (3-trimethoxysilylpropyl) urea, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1,3, 5-tris (3-trimethoxysilylpropyl) isocyanuric acid, or N-tert-butyl-2- (3-trimethoxysilylpropyl) succinimide.
The preparation method of the optical resin composition comprises the following steps:
adding 20-60 parts by weight of solvent into a reaction vessel, then adding 5-15 parts by weight of epoxy acrylic monomer or oligomer thereof heated to more than 60 ℃ and 5-10 parts by weight of photoinitiator, fully and uniformly stirring, then adding 20-40 parts by weight of inorganic nano particles, and continuously and uniformly stirring and mixing at normal temperature to obtain the optical resin composition.
The optical resin composition is a photo-curable coating composition, and is applied by coating, spraying, spin coating, injection, doctor blading, brush coating, nano-imprinting, ink-jet printing, screen printing or pad printing to prepare a molding.
The optical resin composition is applied to OLED, Mini LED and Micro LED display packaging layers, is cured to form a film under the action of heat or ultraviolet light through coating, spraying or ink-jet printing, and the obtained film has a high refractive index (n is more than 1.6 and less than 1.8) and forms a Micro lens array with low refractive index materials (n-1.5).
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an optical resin composition with good ink-jet printing characteristics, which is an organic-inorganic doped composite system constructed by chain or multi-branch epoxy acrylic resin, high-refraction inorganic nano particles, a photoinitiator, a solvent and other functional auxiliaries.
The optical resin composition for the micro-lens array is firstly constructed by adopting the epoxy acrylic resin, can be cured by utilizing the cationic initiator of the epoxy resin and can also be cured by utilizing the free radical of the acrylic resin, and has the advantages of high cohesiveness, high curing speed, good wettability, good miscibility, high glossiness and the like and the ultraviolet curing characteristic.
The long-chain segment can increase the flexibility of the resin, and particularly improve the defects of small tensile strength, poor toughness and the like of the epoxy acrylic resin containing the aromatic group, the aromatic group improves the thermal stability and the refractive index of the resin, and the aromatic group is matched with the inorganic nano particles with high refractive index, the photoinitiator, the solvent and the functional auxiliary agent, so that the optical resin composition is endowed with the performances of high substrate wetting capacity before curing, stable ink-jet printing of a solution system, high refraction, high hardness and high light transmittance after curing.
The invention is an environment-friendly high-refractive-index optical material with less influence on a display device, and the Micro-lens array microstructure is independently manufactured or manufactured together with the low-refractive-index material to be applied to an encapsulation layer applied to display terminals such as OLED (organic light emitting diode), so that the light-emitting efficiency of the prepared display device is improved by more than 20 percent, and the prepared display device is an excellent optical resin composition for the display device and has wide application prospect in the aspects of OLED devices, Mini LED, Micro LED and the like.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Preparation of epoxy acrylic resin monomer:
preparation of intermediate 1:
adding 11.1g of isobutanol, 31.4g of 4-nitrophenylepoxyacrylic acid and 75mL of ethyl acetate into a 250mL reaction device, placing the reaction device into an ice bath, slowly dropwise adding 50mL of ethyl acetate dissolved with 31g N, N' -dicyclohexylcarbodiimide, stirring at low temperature for reaction for 2 hours, returning to room temperature, continuing the reaction for 2 hours, filtering the reaction liquid, leaching a filter cake with ethyl acetate, concentrating an organic phase, and pulping and purifying by using a mixed solution of ethyl acetate and cyclohexane to obtain 32.6g of a target compound, wherein the yield is 82%, and MALDI-TOF-MS (m/z): 265.20.
preparation of intermediate 2:
adding 15.6g of dimethylpropanediol, 33.0g of epoxy acrylic acid and 75mL of ethyl acetate into a 500mL reaction device, placing the reaction device in an ice bath, slowly dropwise adding 125mL of ethyl acetate dissolved with 77g N, N' -dicyclohexylcarbodiimide, stirring at low temperature for reaction for 2h, returning to room temperature, continuing the reaction for 2h, filtering the reaction liquid, leaching a filter cake with ethyl acetate, concentrating an organic phase, and pulping and purifying with a mixed solution of ethyl acetate and cyclohexane to obtain 31.5g of a target compound with the yield of 86%, wherein MALDI-TOF-MS (m/z): 244.30.
preparation of intermediate 3:
adding 15.3g of 1, 1-cyclopropane dimethanol, 61.5g of phenyl epoxy acrylic acid and 75mL of ethyl acetate into a 500mL reaction device, placing the reaction device in an ice bath, slowly dropwise adding 125mL of ethyl acetate dissolved with 77g N, N' -dicyclohexyl carbodiimide, stirring at low temperature for reaction for 2h, recovering to room temperature, continuing to react for 2h, filtering the reaction liquid, leaching a filter cake with ethyl acetate, concentrating an organic phase, pulping and purifying by using a mixed solution of ethyl acetate and cyclohexane to obtain 45.5g of a target compound, wherein the yield is 77%, and MALDI-TOF-MS (m/z): 394.20.
preparation of intermediate 4:
adding 20.4g of pentaerythritol, 58.6g of propyl epoxyacrylic acid and 75mL of ethyl acetate into a 500mL reaction device, placing the reaction device into an ice bath, slowly dropwise adding 150mL of ethyl acetate dissolved with 93g N, N' -dicyclohexylcarbodiimide, stirring at low temperature for reaction for 2h, returning to room temperature, continuing to react for 2h, filtering the reaction liquid, leaching a filter cake with ethyl acetate, concentrating an organic phase, and pulping and purifying with a mixed solution of ethyl acetate and cyclohexane to obtain 50.3g of a target compound with the yield of 71%, wherein MALDI-TOF-MS (m/z): 472.60.
preparation of intermediate 5:
adding 22.5g of triethylene glycol, 33.0g of epoxy acrylic acid and 75mL of ethyl acetate into a 500mL reaction device, placing the reaction device in an ice bath, slowly dropwise adding 125mL of ethyl acetate dissolved with 77g N, N' -dicyclohexylcarbodiimide, stirring at low temperature for reaction for 2h, returning to room temperature, continuing to react for 2h, filtering the reaction liquid, leaching a filter cake with ethyl acetate, concentrating an organic phase, and purifying with a mixed solution of ethyl acetate and cyclohexane to obtain 34.8g of a target compound with the yield of 80%, wherein MALDI-TOF-MS (m/z): 290.50.
preparation of intermediate 6:
adding 24.6g of 2, 2-bis (methoxyethyl) propane-1, 3-diol, 72.8g of methoxyphenyl epoxyacrylic acid and 75mL of ethyl acetate into a 500mL reaction device, placing the reaction device into an ice bath, slowly dropwise adding 125mL of ethyl acetate dissolved with 77g N, N' -dicyclohexylcarbodiimide, stirring and reacting for 2h at low temperature, returning to room temperature, continuing to react for 2h, filtering the reaction solution, leaching a filter cake with ethyl acetate, concentrating an organic phase, and pulping and purifying with a mixed solution of ethyl acetate and cyclohexane to obtain 57.3g of a target compound, wherein the yield is 74%, and MALDI-TOF-MS (m/z): 516.44.
preparation of intermediate 7:
adding 12.3g of dipentaerythritol, 52.8g of epoxy acrylic acid and 37.5mL of ethyl acetate into a 500mL reaction device, placing the reaction device in an ice bath, slowly dropwise adding 150mL of ethyl acetate dissolved with 93g N, N' -dicyclohexylcarbodiimide, stirring at low temperature for reaction for 2h, returning to room temperature, continuing the reaction for 2h, filtering the reaction liquid, leaching a filter cake with ethyl acetate, concentrating an organic phase, and pulping and purifying with a mixed solution of ethyl acetate and cyclohexane to obtain 35.4g of a target compound with the yield of 70%, wherein MALDI-TOF-MS (m/z): 674.65.
preparation of intermediate 8:
adding 34.2g of bisphenol A, 33.0g of epoxy acrylic acid and 75mL of ethyl acetate into a 500mL reaction device, placing the reaction device in an ice bath, slowly dropwise adding 125mL of ethyl acetate dissolved with 77g N, N' -dicyclohexylcarbodiimide, stirring at low temperature for reaction for 2h, returning to room temperature, continuing to react for 2h, filtering the reaction liquid, leaching a filter cake with ethyl acetate, concentrating an organic phase, and purifying with a mixed solution of ethyl acetate and cyclohexane to obtain 47.0g of a target compound, wherein the yield is 85%, and MALDI-TOF-MS (m/z): 368.20.
preparation of intermediate 9:
adding 38.4g of 4,4'- (pentane-3, 3-diyl) diphenol, 66.8g of 3-methyl-3-phenyl epoxy acrylic acid and 75mL of ethyl acetate into a 500mL reaction device, placing the reaction device into an ice bath, slowly dropwise adding 125mL of ethyl acetate dissolved with 77g N, N' -dicyclohexylcarbodiimide, stirring and reacting for 2h at low temperature, returning to room temperature, continuing to react for 2h, filtering the reaction liquid, leaching a filter cake with ethyl acetate, concentrating an organic phase, and pulping and purifying with a mixed solution of ethyl acetate and cyclohexane to obtain 67.4g of a target compound, wherein the yield is 78%, and MALDI-TOF-MS (m/z): 576.35.
preparation of intermediate 10:
adding 46.0g of 1,1, 1-tris (4-hydroxyphenyl) ethane, 69.7g of 3, 3-dimethylepoxyacrylic acid and 75mL of ethyl acetate into a 500mL reaction device, placing the reaction device into an ice bath, slowly dropwise adding 150mL of ethyl acetate dissolved with 93g N, N' -dicyclohexylcarbodiimide, stirring and reacting for 2h at low temperature, returning to room temperature, continuing to react for 2h, filtering the reaction solution, leaching a filter cake with ethyl acetate, concentrating an organic phase, and pulping and purifying with a mixed solution of ethyl acetate and cyclohexane to obtain 67.6g of a target compound, wherein the yield is 75%, and MALDI-TOF-MS (m/z): 600.50.
example 1:
in a reaction apparatus, 50g of propylene glycol monomethyl ether acetate and 50g of cyclohexanone were charged, 20g of intermediate 1 heated to 60 ℃ or higher and 10g of benzoin were charged, and after stirring sufficiently, 80g of ZrO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 2:
in a reaction apparatus, 50g of diethylene glycol monoethyl ether acetate and 50g of propylene glycol methyl ether were charged, 20g of intermediate 1 heated to 60 ℃ or higher and 10g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide were charged, and after stirring them well, 80g of ZrO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 3:
in a reaction apparatus, 60g of propylene glycol monomethyl ether acetate and 40g of ethylene glycol monoethyl ether were charged, 30g of intermediate 2 heated to 60 ℃ or higher and 15g of 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone were charged, and after stirring sufficiently, 60g of GeO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 4:
in a reaction apparatus, after 60g of propylene glycol monomethyl ether acetate and 40g of ethylene glycol monoethyl ether were charged, 30g of intermediate 2 heated to 60 ℃ or higher and 15g of 2-hydroxy-2-methyl-1- (4-hydroxyethoxy) phenyl-1-propanone were charged, and after stirring sufficiently, 60g of ZnS nanoparticles were charged, and stirring was continued at normal temperature to mix sufficiently and uniformly, thereby obtaining the optical resin composition.
Example 5:
in the reaction apparatus, after 40g of diethylene glycol monoethyl ether acetate and 50g of propylene glycol methyl ether were charged, 10g of intermediate 3 heated to 60 ℃ or higher and 10g of polymerized [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] were charged]Acetone (II)]After sufficiently stirring the mixture uniformly, 40g of Ta was added2O5And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 6:
40g of diethylene glycol dipropyl ether and 50g of methyl isopropyl ketone were charged into a reaction apparatus, and 10g of intermediate 3 heated to 60 ℃ or higher and 10g of polymerized [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] were charged into the reaction apparatus]Acetone (II)]After sufficiently and uniformly stirring, 40g of the mixture was pouredTa2O5And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 7:
in a reaction apparatus, 50g of diethylene glycol monoethyl ether acetate and 50g of propylene glycol methyl ether were charged, 20g of intermediate 4 heated to 60 ℃ or higher and 10g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide were charged, and after stirring them well, 80g of ZrO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 8:
in a reaction apparatus, 50g of diethylene glycol monoethyl ether acetate and 50g of propylene glycol methyl ether were charged, 20g of intermediate 4 heated to 60 ℃ or higher and 10g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide were charged, and after stirring them well, 80g of Bi was charged4Ti3O2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 9:
in the reaction apparatus, 60g of diethylene glycol monoethyl ether acetate and 60g of propylene glycol methyl ether were charged, and 30g of intermediate 5 heated to 60 ℃ or higher and 15g of polymerized [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] were charged]Acetone (II)]After sufficiently and uniformly stirring, 80g of ZrO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 10:
in a reaction apparatus, 60g of propylene glycol monomethyl ether acetate and 60g of ethylene glycol monoethyl ether were charged, 30g of intermediate 5 heated to 60 ℃ or higher and 15g of 2-hydroxy-2-methyl-1- (4-hydroxyethoxy) phenyl-1-propanone were charged, and after stirring sufficiently, 80g of Sb was charged2O3And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 11:
in a reaction apparatus, after 100g of propylene glycol monomethyl ether acetate was charged, 20g of intermediate 6 heated to 60 ℃ or higher and 20g of 2, 2-dimethoxy-2-phenylacetophenone were charged, and after stirring them sufficiently and uniformly, 60g of ZnS nanoparticles were charged and stirred continuously at room temperature to mix them sufficiently and uniformly, thereby obtaining the optical resin composition.
Example 12:
in a reaction apparatus, 50g of diethylene glycol monoethyl ether acetate and 50g of propylene glycol methyl ether were charged, 20g of intermediate 6 heated to 60 ℃ or higher and 20g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide were charged, and after stirring sufficiently and uniformly, 60g of Bi was charged4Ti3O2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 13:
in the reaction apparatus, 60g of diethylene glycol monoethyl ether acetate and 60g of propylene glycol monomethyl ether were charged, and 30g of intermediate 7 heated to 60 ℃ or higher and 15g of polymerized [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] were charged]Acetone (II)]After sufficiently and uniformly stirring, 80g of ZrO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 14:
in a reaction apparatus, after 60g of propylene glycol monomethyl ether acetate and 60g of propylene glycol monomethyl ether were charged, 30g of intermediate 7 heated to 60 ℃ or higher and 15g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide were charged, and after stirring sufficiently and uniformly, 80g of HfO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 15:
in the reaction apparatus, 60g of diethylene glycol monoethyl ether acetate and 60g of propylene glycol monomethyl ether were charged, and 30g of intermediate 7 heated to 60 ℃ or higher and 15g of polymerized [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] were charged]Acetone (II)]10g of 1,1,2, 2-tetrafluorooctylhexyl ether and 20g of polyether-modified polydimethylsiloxane, and after sufficiently and uniformly stirring, 80g of ZrO was put into the mixture2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 16:
50g of diethylene glycol monoethyl ether acetate and 50g of diethylene glycol monomethyl ether were charged into a reaction apparatus, 20g of intermediate 8 heated to 60 ℃ or higher and 10g of 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone were charged, and after stirring sufficiently, 40g of CeO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 17:
in a reaction apparatus, 50g of propylene glycol monomethyl ether acetate and 50g of ethylene glycol monoethyl ether were charged, 20g of intermediate 8 heated to 60 ℃ or higher and 10g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide were charged, and after stirring them well, 40g of CeO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 18:
in a reaction apparatus, 50g of propylene glycol monomethyl ether acetate and 50g of ethylene glycol monoethyl ether were charged, 20g of intermediate 8 heated to 60 ℃ or higher and 10g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, 10g of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane and 10g of BYK-057 from Bick chemical Co., Germany were charged, and after stirring sufficiently and uniformly, 40g of CeO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 19
In a reaction apparatus, after 40g of ethylene glycol monomethyl ether acetate and 40g of propylene glycol were charged, 10g of intermediate 9 heated to 60 ℃ or higher and 10g of 2-hydroxy-2-methyl-1- (4-hydroxyethoxy) phenyl-1-propanone were charged, and after stirring sufficiently and uniformly, 60g of Nb were charged2O5And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 20:
in a reaction apparatus, 80g of ethylene glycol monomethyl ether acetate was charged, 10g of intermediate 9 heated to 60 ℃ or higher and 10g of 2-hydroxy-2-methyl-1- (4-hydroxyethoxy) phenyl-1-propanone were charged, and after stirring sufficiently, 60g of Nb was charged2O5And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 21:
in the reaction apparatus, 60g of diethylene glycol monoethyl ether acetate and 60g of propylene glycol monomethyl ether were charged, 10g of intermediate 10 heated to 60 ℃ or higher and 15g of polymerized [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] methyl ether]Acetone (II)]After sufficiently and uniformly stirring, 80g of ZrO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 22:
in a reaction apparatus, 50g of diethylene glycol monoethyl ether acetate and 40g of propylene glycol monomethyl ether were charged, 30g of intermediate 10 heated to 60 ℃ or higher and 15g of polymerized [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] methyl ether were charged]Acetone (II)]After sufficiently and uniformly stirring, 80g of ZrO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Example 23:
in a reaction apparatus, 50g of diethylene glycol monoethyl ether acetate and 40g of propylene glycol monomethyl ether were charged, 30g of intermediate 10 heated to 60 ℃ or higher and 15g of polymerized [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] methyl ether were charged]Acetone (II)]20g of 1,1,2, 2-tetrafluorooctylhexyl ether and 10g of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane were sufficiently and uniformly stirred, and 80g of ZrO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Comparative example 1
In a reaction apparatus, 60g of diethylene glycol monoethyl ether acetate and 60g of propylene glycol monomethyl ether were charged, and 30g of a polypentadiene heated to 60 ℃ or higher was chargedTetraol hexa (meth) acrylate and 15g of polymerized [ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ]]Acetone (II)]After sufficiently and uniformly stirring, 80g of ZrO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Comparative example 2
In a reaction apparatus, 50g of propylene glycol monomethyl ether acetate and 50g of ethylene glycol monoethyl ether were charged, 20g of bisphenol A dimethacrylate heated to 60 ℃ or higher and 10g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide were charged, and after stirring them well, 40g of CeO was charged2And (3) continuously stirring the nano particles at normal temperature to fully and uniformly mix the nano particles to obtain the optical resin composition.
Viscosity was measured using a viscometer for the optical resin compositions in examples 1 to 23 and comparative examples 1 and 2, refractive index of the thin film was measured using an abbe refractometer and coated to a thickness of 5um to a quartz substrate using an inkjet printing technique, and after drying the substrate in a vacuum drying oven for 30 minutes, the substrate was put into a UV curing machine at about 2000mJ/cm2The optical resin composition was irradiated to be cured to form a high refractive film, light transmittance of the film was measured using a transmittance tester for the optical film, cured hardness of the optical material was measured using a durometer, and the results are described in table 1 below.
TABLE 1
Serial number
Examples
Viscosity (cps)
Refractive [email protected]
Light transmittance
Hardness (H)
1
Example 1
9.2
1.62
88％
0.9
2
Example 2
9.5
1.63
88％
1.0
3
Example 3
10.4
1.65
91％
1.0
4
Example 4
10.4
1.68
87％
0.9
5
Example 5
11.6
1.63
90％
1.0
6
Example 6
11.2
1.63
89％
1.0
7
Example 7
11.0
1.65
94％
1.2
8
Example 8
11.3
1.67
92％
1.0
9
Example 9
9.6
1.60
86％
0.9
10
Example 10
9.4
1.57
85％
0.9
11
Example 11
11.5
1.61
87％
1.0
12
Example 12
11.1
1.62
93％
1.1
13
Example 13
10.8
1.65
96％
1.1
14
Example 14
10.3
1.62
94％
1.0
15
Example 15
10.0
1.64
94％
1.2
16
Example 16
12.0
1.60
91％
1.0
17
Example 17
11.8
1.60
90％
1.0
18
Example 18
11.5
1.62
92％
1.1
19
Example 19
12.0
1.67
94％
1.3
20
Example 20
12.5
1.70
91％
1.3
21
Example 21
11.2
1.66
90％
1.1
22
Example 22
11.6
1.68
94％
1.2
23
Example 23
11.3
1.65
93％
1.1
24
Comparative example 1
7.5
1.77
70％
0.7
25
Comparative example 2
9.0
1.50
80％
0.6
As can be seen from the above table, compared with the optical resin composition prepared by the acrylic resin and the optical resin composition prepared by the optical resin in the prior art, the optical resin composition constructed by the chain or multi-branch epoxy acrylic resin, the high-refraction inorganic nano particles, the photoinitiator, the solvent and other functional additives has the advantages that the refractive index is between that of a glass substrate (1.55) and that of an ITO electrode (1.8-2.1), the light transmittance is higher, the hardness is better, the problems of inorganic nano particle agglomeration and organic polymer solubility are obviously improved, the shrinkage cavity resistance and the substrate wetting capacity are good, the optical resin composition can be used between the electrode and the light-emitting interface of an OLED display device, a Mini LED, a Micro LED and the like, the light-emitting path is improved by increasing the critical angle of the light-emitting device, the total reflection is reduced, the light-emitting efficiency is improved, and the optical resin composition can be printed by ink-jet printing, The film is prepared by cold process with less influence on the display device such as silk-screen printing, and is a more excellent optical material for the display device.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
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