CN113249039A - Optical adhesive - Google Patents
Optical adhesive Download PDFInfo
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- CN113249039A CN113249039A CN202110666389.3A CN202110666389A CN113249039A CN 113249039 A CN113249039 A CN 113249039A CN 202110666389 A CN202110666389 A CN 202110666389A CN 113249039 A CN113249039 A CN 113249039A
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides an optical adhesive, which relates to the technical field of optical adhesives and comprises the following components in parts by weight: 30-40 parts of o-phenylphenoxyethyl acrylate, 20-30 parts of ethoxylated bisphenol A dimethacrylate, 10-20 parts of tetrahydrofurfuryl alcohol acrylate, 10-20 parts of trihydroxymethyl cyclohexyl acrylate, 5-10 parts of bisphenol fluorene acrylate, 1-5 parts of organic-inorganic hybrid acrylate, 0.1-1 part of antioxidant, 1-5 parts of initiator and 0.5-2 parts of organic silicon assistant. The adhesive adopts various monomers with high refractive index, and generates synergistic effect with a coupling agent, a photoinitiator and an antioxidant, so that the uniformity of the curing reaction of the liquid optical adhesive and the refractive index after curing are improved, and the liquid optical adhesive has good refractive index, hardness and mechanical property and good yellowing resistance.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of optical adhesives, in particular to an optical adhesive.
[ background of the invention ]
In recent years, with the development of the electronic industry, the variety of optical electronic products is more and more, and the optical adhesive is more and more demanded as a matching product of the electronic industry, but the demand is higher and higher. The optical adhesive is a high molecular substance which has optical performance similar to that of an optical part and has good adhesive performance. The adhesive can bond two or more optical parts into an optical component which can meet the optical design requirements, such as bonding optical polarization elements such as an optical filter and a polarizing film by using the adhesive and is used for optical fiber coating adhesive. Many high-end optical applications use glues to place high demands on optical adhesives: the adhesive is colorless and transparent, the light transmittance in a specified light band is more than 90%, and the refractive index of the cured adhesive layer is close to the shading coefficient of the adhesive and the optical element.
The use requirements of optical adhesives are diverse. In the application of optical and electronic products, particularly optical glasses products, the refractive index of the adhesive film has great influence on the product performance, the higher the refractive index is, the thinner the optical glasses are, and the wider the visual field of the optical glasses are. And the difference in refractive index has a great influence on the light extraction efficiency. When light passes through materials such as a mirror surface, a total reflection effect occurs on an interface of the light, most of the light is reflected back to the inside and cannot be effectively guided out, and the brightness efficiency is directly damaged. In order to more effectively reduce the light loss caused by interface refraction, the light extraction efficiency is improved as much as possible. The refractive index of the adhesive film and the lens material is required to be as high as possible, so that the refractive index difference of the high-refractive-index light-transmitting adhesive is crucial.
The existing optical adhesive has poor refractive index, and often causes the adhesive film to be too thick, thereby affecting the quality. Most of optical adhesives made in China in the market at present have a refractive index of below 1.50, mainly comprise acrylate, epoxy resin, epoxy acrylic resin, polyurethane acrylate and the like, and optical materials higher than 1.5 are few, and the performances of yellowing resistance, high temperature resistance, scratch resistance and the like still need to be improved.
[ summary of the invention ]
In view of the above, the present invention is to provide an optical adhesive, which has high refractive index, fast curing speed, scratch resistance and no easy yellowing.
In order to solve the technical problems, the invention adopts the following technical scheme:
the optical adhesive comprises the following components in parts by weight: 30-40 parts of o-phenylphenoxyethyl acrylate, 20-30 parts of ethoxylated bisphenol A dimethacrylate, 10-20 parts of tetrahydrofurfuryl alcohol acrylate, 10-20 parts of trihydroxymethyl cyclohexyl acrylate, 5-10 parts of bisphenol fluorene acrylate, 1-5 parts of organic-inorganic hybrid acrylate, 0.1-1 part of antioxidant, 1-5 parts of initiator and 0.5-2 parts of organic silicon assistant.
Preferably, the organic-inorganic hybrid acrylate is nano silicon dioxide organic-inorganic hybrid acrylate, nano titanium dioxide organic-inorganic hybrid acrylate and nano zirconium oxide organic-inorganic hybrid acrylate.
Further, the preparation method of the nano-silica organic-inorganic hybrid acrylate or the nano-zirconia organic-inorganic hybrid acrylate comprises the following steps: and mixing the acrylate resin, the nano silicon dioxide sol/nano titanium dioxide sol/nano zirconium dioxide sol, and stirring for 0.5-3 h to obtain the nano silicon dioxide organic-inorganic hybrid acrylate or the nano zirconium oxide organic-inorganic hybrid acrylate.
Further, the nano-silica sol is modified by gamma- (methacryloyloxy) propyl trimethoxy silane, and then the modified nano-silica sol is mixed with alkenoic acid ester resin to prepare the nano-silica organic-inorganic hybrid acrylate.
Preparing nano-silica sol by adopting a sol-gel method, mixing gamma- (methacryloyloxy) propyl trimethoxy silane and absolute ethyl alcohol, pouring the mixture into the nano-silica sol, reacting for 4-6 hours at 40-50 ℃, adding a proper amount of deionized water after the reaction is finished, dropwise adding a proper amount of hydrochloric acid solution, neutralizing to be neutral, standing overnight, centrifuging to obtain gel, washing with absolute ethyl alcohol for multiple times to remove gamma- (methacryloyloxy) propyl trimethoxy silane hydrolysate which is not grafted until the washed liquid can not fade the acidic potassium permanganate solution. And (3) drying the mixture for 20-30 hours in vacuum at the temperature of 40-50 ℃ to obtain the modified nano silicon dioxide.
Further, the nano-zirconia is modified by 3-aminopropyltrimethoxysilane and octylphenol polyoxyethylene ether to obtain modified nano-zirconia, modified nano-zirconia sol is prepared, and finally the modified nano-zirconia is mixed with olefine acid ester resin to prepare the nano-zirconia organic-inorganic hybrid acrylate.
And (2) drying the nano zirconia in a vacuum drying oven for 2 hours, adding acetone, performing ultrasonic oscillation for 20 minutes, adding 3-aminopropyltrimethoxysilane and octylphenol polyoxyethylene ether, stirring for reaction, performing centrifugal separation, washing for 3 times by using acetone, and finally performing vacuum drying for 20-30 hours at the temperature of 40-50 ℃ to obtain the modified nano zirconia.
Preparing modified nano zirconia sol by a sol-gel method, and finally mixing the modified nano zirconia sol with olefine acid ester resin to prepare the nano zirconia organic-inorganic hybrid acrylate.
Preferably, the antioxidants are antioxidant 1010 and antioxidant 1790. Tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid, tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
The antioxidant is used for blocking the oxidation reaction of each component in the optical adhesive under the environment of heating, illumination or oxygen so as to delay the yellowing process of the optical adhesive. According to the applicability of a polymerization monomer, the antioxidant is selected from tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and a physical barrier layer can be formed on the surface of the optical adhesive, so that oxygen can be prevented from permeating from air, the oxidation of the surface layer of the optical adhesive can be inhibited, and the yellowing reaction of the optical adhesive can be avoided.
When the amount of the antioxidant is too small, the amount of the antioxidant is insufficient to capture radicals generated by thermal decomposition, and when the amount of the antioxidant is large, the excessive amount of the antioxidant captures radicals generated from the photoinitiator during photocuring to reduce the reaction rate and the degree of crosslinking, resulting in a decrease in high temperature resistance thereof.
Preferably, the organosilicon adjuvant is KH 560.
The assistant is an organic silicon coupling agent, so that the bonding performance is improved, if the addition amount is small, the coupling agent cannot be contacted with the whole bonded surface interface, and the improved bonding force is insufficient; if the amount of the silane coupling agent added is too large, the silane coupling agent is contained in the adhesive interface between the adhesive and the adhesive, and the silane coupling agent is liable to undergo a condensation reaction with moisture, resulting in a decrease in the adhesive strength of the adhesive surface.
Preferably, the initiator is any one or a mixture of more than one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 4-phenyl benzophenone, 2-ethylhexyl-4-dimethylamine benzoate and ethyl-4-dimethylamine benzoate.
The photoinitiator is an indispensable component of the photocurable adhesive and has a decisive effect on the curing rate of the system. The photoinitiator generates active free radicals or cations after absorbing ultraviolet light or visible light energy, and initiates the polymerization of double bonds in the prepolymer or the active monomer.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the optical adhesive disclosed by the invention is high in refractive index, high in curing speed, scratch-resistant and not easy to yellow.
The liquid optical adhesive adopts various monomers with high refractive index, and generates synergistic effect with a coupling agent, a photoinitiator and an antioxidant, so that the uniformity of the curing reaction of the liquid optical adhesive and the refractive index after curing are improved, and the liquid optical adhesive has good refractive index, hardness and mechanical property and good yellowing resistance. The bisphenol A dimethacrylate cured film has high hardness, high refractive index, good heat resistance and electrical property, but poor light aging resistance and yellowing resistance, and can improve the yellowing resistance effect and improve the mechanical property by combining bisphenol fluorene acrylate, organic-inorganic hybrid acrylate and antioxidant.
2. The optical adhesive provided by the invention has the advantages that the viscosity, the refractive index, the mechanical property after curing and the optical property of a comprehensive product are optimal by using a plurality of monomers, other types can be used, and the product performance is embrittled or the viscosity is slightly larger or slightly smaller, so that the construction is not facilitated. The bisphenol fluorene acrylate is an optical resin material monomer with high refractive index, yellowing resistance and other properties, so that the light-cured resin has high transparency. The antioxidant is used for blocking the oxidation reaction of each component in the optical adhesive under the environment of heating, illumination or oxygen so as to delay the yellowing process of the optical adhesive. The antioxidants tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester can form a physical barrier layer on the surface of the optical adhesive, so that oxygen can be prevented from permeating from air, the oxidation of the surface layer of the optical adhesive is inhibited, and the yellowing reaction of the optical adhesive is avoided.
3. According to the optical adhesive, the organic-inorganic hybrid acrylate resin is added, the performance advantages of the organic polymer and the inorganic nanoparticles are combined, the adhesive physical performance can be improved, and the hardness, the thermal stability and the scratch resistance of the adhesive are improved. Simultaneous TiO 22The optical adhesive has high chemical stability and high refractive index, has high transparency and low absorption in visible and near infrared regions, and can also improve the refractive index of the optical adhesive. The zirconia can particularly remarkably improve the hardness and the wear resistance of the optical adhesive. The nano silicon dioxide, titanium dioxide and nano zirconia are not easy to be uniformly dispersed among high molecular chains, not only can not play a role in strengthening and toughening, but also can damage the mechanical property of a polymer matrix. Therefore, the surface modification is carried out on the nano silicon dioxide and the nano zirconium oxide firstly, so that the agglomeration tendency of groups can be effectively reduced, the dispersibility of the nano silicon dioxide and the nano zirconium oxide in an organic phase can be improved, and the mechanical property of the colloid can be better improved.
[ detailed description ] embodiments
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The optical adhesive comprises the following components in parts by weight: 30 parts of o-phenyl phenoxyethyl acrylate, 20 parts of ethoxylated bisphenol A dimethacrylate, 10 parts of tetrahydrofurfuryl alcohol acrylate, 10 parts of trihydroxymethyl cyclohexyl acrylate, 8 parts of bisphenol fluorene acrylate, 3 parts of organic-inorganic hybrid acrylate, 0.5 part of antioxidant, 2 parts of initiator and 1 part of organic silicon assistant.
The organic-inorganic hybrid acrylate nano silicon dioxide organic-inorganic hybrid acrylate, the nano titanium dioxide organic-inorganic hybrid acrylate and the nano zirconium oxide organic-inorganic hybrid acrylate.
The preparation method of the nano silicon dioxide organic-inorganic hybrid acrylate or the nano zirconium oxide organic-inorganic hybrid acrylate comprises the following steps: mixing acrylate resin, nano silicon dioxide sol/nano titanium dioxide sol/nano zirconium dioxide sol, and stirring for 2 hours to obtain nano silicon dioxide organic-inorganic hybrid acrylate or nano zirconium oxide organic-inorganic hybrid acrylate. Wherein the content of the nano silicon dioxide sol, the nano titanium dioxide sol and the nano zirconium dioxide sol is 10 percent.
The antioxidant is tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
The organic silicon assistant is KH 560. The initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Example 2
The optical adhesive comprises the following components in parts by weight: 30 parts of o-phenyl phenoxyethyl acrylate, 20 parts of ethoxylated bisphenol A dimethacrylate, 10 parts of tetrahydrofurfuryl alcohol acrylate, 10 parts of trihydroxymethyl cyclohexyl acrylate, 8 parts of bisphenol fluorene acrylate, 3 parts of organic-inorganic hybrid acrylate, 0.5 part of antioxidant, 2 parts of initiator and 1 part of organic silicon assistant.
The organic-inorganic hybrid acrylate is nano silicon dioxide organic-inorganic hybrid acrylate, nano titanium dioxide organic-inorganic hybrid acrylate and nano zirconium oxide organic-inorganic hybrid acrylate.
The preparation method of the nano silicon dioxide organic-inorganic hybrid acrylate or the nano zirconium oxide organic-inorganic hybrid acrylate comprises the following steps: mixing acrylate resin, nano silicon dioxide sol/nano titanium dioxide sol/nano zirconium dioxide sol, and stirring for 2 hours to obtain nano silicon dioxide organic-inorganic hybrid acrylate or nano zirconium oxide organic-inorganic hybrid acrylate. Wherein the content of the nano silicon dioxide sol, the nano titanium dioxide sol and the nano zirconium dioxide sol is 10 percent.
The antioxidant is tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester. The organic silicon assistant is KH 560. The initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Firstly, modifying the nano-silica sol by using gamma- (methacryloxy) propyl trimethoxy silane, and then mixing the modified nano-silica sol with olefine acid ester resin to prepare the nano-silica organic-inorganic hybrid acrylate.
Preparing nano silica sol by adopting a sol-gel method, mixing 20ml of gamma- (methacryloyloxy) propyl trimethoxy silane and 30ml of absolute ethyl alcohol, pouring the mixture into 30ml of nano silica sol, reacting at 45 ℃ for 5 hours, adding a proper amount of deionized water after the reaction is finished, dropwise adding a proper amount of hydrochloric acid solution, neutralizing to be neutral, standing overnight, centrifuging to obtain gel, washing with absolute ethyl alcohol for multiple times to remove gamma- (methacryloyloxy) propyl trimethoxy silane hydrolysate which is not grafted until the washed liquid can not fade the acidic potassium permanganate solution. And (3) drying for 25h in vacuum at the temperature of 45 ℃ to obtain the modified nano silicon dioxide.
Example 3
The optical adhesive comprises the following components in parts by weight: 30 parts of o-phenyl phenoxyethyl acrylate, 20 parts of ethoxylated bisphenol A dimethacrylate, 10 parts of tetrahydrofurfuryl alcohol acrylate, 10 parts of trihydroxymethyl cyclohexyl acrylate, 8 parts of bisphenol fluorene acrylate, 3 parts of organic-inorganic hybrid acrylate, 0.5 part of antioxidant, 2 parts of initiator and 1 part of organic silicon assistant.
The antioxidant is tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester. The organic silicon assistant is KH 560. The initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The organic-inorganic hybrid acrylate is nano silicon dioxide organic-inorganic hybrid acrylate, nano titanium dioxide organic-inorganic hybrid acrylate and nano zirconium oxide organic-inorganic hybrid acrylate.
The preparation method of the nano silicon dioxide organic-inorganic hybrid acrylate or the nano zirconium oxide organic-inorganic hybrid acrylate comprises the following steps: mixing acrylate resin, nano silicon dioxide sol/nano titanium dioxide sol/nano zirconium dioxide sol, and stirring for 2 hours to obtain nano silicon dioxide organic-inorganic hybrid acrylate or nano zirconium oxide organic-inorganic hybrid acrylate. Wherein the content of the nano silicon dioxide sol, the nano titanium dioxide sol and the nano zirconium dioxide sol is 10 percent.
Firstly, 3-aminopropyl trimethoxy silane, polyethylene glycol and octylphenol polyoxyethylene ether are used for modifying nano zirconia to obtain modified nano zirconia, modified nano zirconia sol is prepared, and finally the modified nano zirconia is mixed with olefine acid ester resin to prepare the nano zirconia organic-inorganic hybrid acrylate. The method comprises the following specific steps: and (2) putting 10g of nano zirconia into a vacuum drying oven for drying for 2h, adding 500ml of acetone for ultrasonic oscillation for 20min, then adding 10g of 3-aminopropyltrimethoxysilane and 5g of octylphenol polyoxyethylene ether, stirring for reaction, performing centrifugal separation, washing for 3 times by using acetone, and finally performing vacuum drying for 24h at the temperature of 45 ℃ to obtain the modified nano zirconia. Preparing modified nano zirconia sol by a sol-gel method, and finally mixing the modified nano zirconia sol with olefine acid ester resin to prepare the nano zirconia organic-inorganic hybrid acrylate.
Example 4
The optical adhesive comprises the following components in parts by weight: 30 parts of o-phenyl phenoxyethyl acrylate, 20 parts of ethoxylated bisphenol A dimethacrylate, 10 parts of tetrahydrofurfuryl alcohol acrylate, 10 parts of trihydroxymethyl cyclohexyl acrylate, 8 parts of bisphenol fluorene acrylate, 3 parts of organic-inorganic hybrid acrylate, 0.5 part of antioxidant, 2 parts of initiator and 1 part of organic silicon assistant.
The antioxidant is tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester. The organic silicon assistant is KH 560. The initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The organic-inorganic hybrid acrylate is nano silicon dioxide organic-inorganic hybrid acrylate, nano titanium dioxide organic-inorganic hybrid acrylate and nano zirconium oxide organic-inorganic hybrid acrylate.
The preparation method of the nano silicon dioxide organic-inorganic hybrid acrylate or the nano zirconium oxide organic-inorganic hybrid acrylate comprises the following steps: mixing acrylate resin, nano silicon dioxide sol/nano titanium dioxide sol/nano zirconium dioxide sol, and stirring for 2 hours to obtain nano silicon dioxide organic-inorganic hybrid acrylate or nano zirconium oxide organic-inorganic hybrid acrylate. Wherein the content of the nano silicon dioxide sol, the nano titanium dioxide sol and the nano zirconium dioxide sol is 10 percent.
Firstly, modifying the nano-silica sol by using gamma- (methacryloxy) propyl trimethoxy silane, and then mixing the modified nano-silica sol with olefine acid ester resin to prepare the nano-silica organic-inorganic hybrid acrylate.
Preparing nano silica sol by adopting a sol-gel method, mixing 20ml of gamma- (methacryloyloxy) propyl trimethoxy silane and 30ml of absolute ethyl alcohol, pouring the mixture into 30ml of nano silica sol, reacting at 45 ℃ for 5 hours, adding a proper amount of deionized water after the reaction is finished, dropwise adding a proper amount of hydrochloric acid solution, neutralizing to be neutral, standing overnight, centrifuging to obtain gel, washing with absolute ethyl alcohol for multiple times to remove gamma- (methacryloyloxy) propyl trimethoxy silane hydrolysate which is not grafted until the washed liquid can not fade the acidic potassium permanganate solution. And (3) drying for 25h in vacuum at the temperature of 45 ℃ to obtain the modified nano silicon dioxide.
Firstly, 3-aminopropyl trimethoxy silane, polyethylene glycol and octylphenol polyoxyethylene ether are used for modifying nano zirconia to obtain modified nano zirconia, modified nano zirconia sol is prepared, and finally the modified nano zirconia is mixed with olefine acid ester resin to prepare the nano zirconia organic-inorganic hybrid acrylate. The method comprises the following specific steps: and (2) putting 10g of nano zirconia into a vacuum drying oven for drying for 2h, adding 500ml of acetone for ultrasonic oscillation for 20min, then adding 10g of 3-aminopropyltrimethoxysilane and 5g of octylphenol polyoxyethylene ether, stirring for reaction, performing centrifugal separation, washing for 3 times by using acetone, and finally performing vacuum drying for 24h at the temperature of 45 ℃ to obtain the modified nano zirconia. Then preparing modified nano zirconia sol by adopting a sol-gel method, and finally mixing the modified nano zirconia sol with olefine acid ester resin to prepare the nano zirconia organic-inorganic hybrid acrylate.
Comparative example 1
The optical adhesive comprises the following components in parts by weight: 30 parts of o-phenyl phenoxyethyl acrylate, 20 parts of ethoxylated bisphenol A dimethacrylate, 10 parts of tetrahydrofurfuryl alcohol acrylate, 10 parts of trihydroxymethyl cyclohexyl acrylate, 8 parts of bisphenol fluorene acrylate, 0.5 part of antioxidant, 2 parts of initiator and 1 part of organic silicon assistant.
The antioxidant is tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester. The organic silicon assistant is KH 560. The initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Comparative example 2
Compared with the comparative example 1, the organic-inorganic hybrid acrylate is nano silicon dioxide organic-inorganic hybrid acrylate and nano zirconium oxide organic-inorganic hybrid acrylate with the mass ratio of 1:1, and the rest are the same.
Comparative example 3
Compared with the comparative example 1, the organic-inorganic hybrid acrylate is the nano titanium dioxide organic-inorganic hybrid acrylate and the nano zirconium oxide organic-inorganic hybrid acrylate with the mass ratio of 1:1, and the rest are the same.
Comparative example 4
Compared with the comparative example 1, the organic-inorganic hybrid acrylate is nano silicon dioxide organic-inorganic hybrid acrylate and nano titanium dioxide organic-inorganic hybrid acrylate with the mass ratio of 1:1, and the other components are the same.
Comparative example 5
The optical adhesive comprises the following components in parts by weight: 30 parts of o-phenyl phenoxyethyl acrylate, 20 parts of ethoxylated bisphenol A dimethacrylate, 10 parts of tetrahydrofurfuryl alcohol acrylate, 10 parts of trihydroxymethyl cyclohexyl acrylate, 8 parts of bisphenol fluorene acrylate, 5 parts of organic-inorganic hybrid acrylate, 0.5 part of antioxidant, 2 parts of initiator and 1 part of organic silicon assistant.
The antioxidant is tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester. The organic silicon assistant is KH 560. The initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone. The organic-inorganic hybrid acrylate is nano silicon dioxide organic-inorganic hybrid acrylate, nano titanium dioxide organic-inorganic hybrid acrylate and nano zirconium oxide organic-inorganic hybrid acrylate.
Comparative example 6
The optical adhesive comprises the following components in parts by weight: 30 parts of o-phenyl phenoxyethyl acrylate, 20 parts of ethoxylated bisphenol A dimethacrylate, 10 parts of tetrahydrofurfuryl alcohol acrylate, 10 parts of trihydroxymethyl cyclohexyl acrylate, 8 parts of bisphenol fluorene acrylate, 6 parts of organic-inorganic hybrid acrylate, 0.5 part of antioxidant, 2 parts of initiator and 1 part of organic silicon assistant.
The antioxidant is tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester. The organic silicon assistant is KH 560. The initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone. The organic-inorganic hybrid acrylate is nano silicon dioxide organic-inorganic hybrid acrylate, nano titanium dioxide organic-inorganic hybrid acrylate and nano zirconium oxide organic-inorganic hybrid acrylate.
Comparative example 7
The optical adhesive comprises the following components in parts by weight: 30 parts of o-phenyl phenoxyethyl acrylate, 20 parts of ethoxylated bisphenol A dimethacrylate, 10 parts of tetrahydrofurfuryl alcohol acrylate, 10 parts of trihydroxymethyl cyclohexyl acrylate, 8 parts of bisphenol fluorene acrylate, 3 parts of organic-inorganic hybrid acrylate, 2 parts of an initiator and 1 part of an organic silicon assistant.
The organic silicon assistant is KH 560. The initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone. The organic-inorganic hybrid acrylate is nano silicon dioxide organic-inorganic hybrid acrylate, nano titanium dioxide organic-inorganic hybrid acrylate and nano zirconium oxide organic-inorganic hybrid acrylate.
Comparative example 8
The optical adhesive comprises the following components in parts by weight: 30 parts of o-phenyl phenoxyethyl acrylate, 20 parts of ethoxylated bisphenol A dimethacrylate, 10 parts of tetrahydrofurfuryl alcohol acrylate, 10 parts of trihydroxymethyl cyclohexyl acrylate, 3 parts of organic-inorganic hybrid acrylate, 2 parts of an initiator and 1 part of an organic silicon assistant.
The antioxidant is tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester. The organic silicon assistant is KH 560. The initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone. The organic-inorganic hybrid acrylate is nano silicon dioxide organic-inorganic hybrid acrylate and nano zirconium oxide organic-inorganic hybrid acrylate.
Experimental verification
1. The experimental method comprises the following steps: optical adhesives were prepared using the formulations of examples 1-3 and comparative examples 1-5, respectively, and compared to commercially available optical adhesives.
2. The detection method comprises the following steps:
2.1 refractive index test method: according to the determination of the national standard GB/T614-2006 general method for determining the refractive index of chemical reagents, the Abbe refractometer is used for testing.
2.2 light transmittance test method: the light transmittance and haze are measured by a light transmittance and haze tester according to the national standard GB/T2410-2008 'determination of transparent plastic light transmittance and haze'.
2.3 elongation at break: measured by a universal tensile tester. The dumbbell test pieces were cured by irradiation with a halogen lamp or a high-pressure mercury lamp of 2500mj/cm 2. The liquid optical adhesive is cured between an organic glass test piece and a glass test piece to prepare a test piece, and the test piece is also measured by a universal tensile testing machine.
2.4 test for Shore D: measured according to standard astm D2240 using a shore durometer D type 0-100 HD.
2.5 yellowing resistance: the sample was placed in a UV aging oven at 60 ℃ and 0.86w/cm2 for 500 hours and the yellow index of the aged sample was measured.
3. And (3) detection results: see Table 1
TABLE 1 statistics of results
As can be seen from Table 1, the optical adhesive of the present invention has high refractive index, fast curing speed, scratch resistance and no easy yellowing.
Examples 1-3 can see that the organic-inorganic hybrid acrylate can significantly improve the hardness, elongation at break and anti-yellowing effect of the optical adhesive. And the surface modification is carried out on the nano silicon dioxide, the titanium dioxide and the nano zirconia, so that the agglomeration tendency of groups can be effectively reduced, the dispersibility of the nano silicon dioxide, the titanium dioxide and the nano zirconia in an organic phase can be improved, and the mechanical property of the colloid can be better improved.
In comparative examples 1 to 4, it can be seen that the nano silica, titanium dioxide and nano zirconia are combined with the acrylate to comprehensively improve the physical and mechanical properties of the colloid in terms of refractive index, mechanical properties and the like, thereby improving the hardness, thermal stability and scratch resistance of the colloid.
Comparative examples 5 to 6 show that an excessive amount of organic-inorganic hybrid acrylate affects the light transmittance of the optical adhesive, and thus, the amount should be strictly controlled.
Comparative example 7 contains no antioxidant, and the anti-yellowing effect is reduced. The comparative example 8 does not contain bisphenol fluorene acrylate, the anti-yellowing effect is reduced, and the organic-inorganic hybrid acrylate can achieve better anti-yellowing effect under the combined action of the antioxidant and the bisphenol fluorene acrylate.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. The optical adhesive is characterized by comprising the following components in parts by weight: 30-40 parts of o-phenylphenoxyethyl acrylate, 20-30 parts of ethoxylated bisphenol A dimethacrylate, 10-20 parts of tetrahydrofurfuryl alcohol acrylate, 10-20 parts of trihydroxymethyl cyclohexyl acrylate, 5-10 parts of bisphenol fluorene acrylate, 1-5 parts of organic-inorganic hybrid acrylate, 0.1-1 part of antioxidant, 1-5 parts of initiator and 0.5-2 parts of organic silicon assistant.
2. The optical adhesive according to claim 1, wherein the organic-inorganic hybrid acrylate is nano-silica organic-inorganic hybrid acrylate, nano-titania organic-inorganic hybrid acrylate and nano-zirconia organic-inorganic hybrid acrylate.
3. The optical adhesive according to claim 2, wherein the preparation method of the nano-silica organic-inorganic hybrid acrylate, the nano-titania organic-inorganic hybrid acrylate or the nano-zirconia organic-inorganic hybrid acrylate comprises the following steps: and mixing the acrylate resin, the nano silicon dioxide sol/nano titanium dioxide sol/nano zirconia sol, and stirring for 0.5-3 h to obtain the nano silicon dioxide organic-inorganic hybrid acrylate or the nano zirconia organic-inorganic hybrid acrylate.
4. The optical adhesive according to claim 3, wherein the nano-silica organic-inorganic hybrid acrylate is prepared by modifying nano-silica sol with gamma- (methacryloyloxy) propyltrimethoxysilane and then mixing with the acrylate resin.
5. The optical adhesive according to claim 3, wherein the nano zirconia is modified by 3-aminopropyltrimethoxysilane and octylphenol polyoxyethylene ether to obtain modified nano zirconia, a modified nano zirconia sol is prepared, and finally the modified nano zirconia is mixed with an alkenoic acid ester resin to prepare the nano zirconia organic-inorganic hybrid acrylate.
6. The optical adhesive according to claim 1, wherein the antioxidants are tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanuric acid and pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
7. The optical adhesive according to claim 1, wherein the silicone additive is KH 560.
8. The optical adhesive according to claim 1, wherein the initiator is any one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 4-phenyl benzophenone, 2-ethylhexyl-4-dimethylamine benzoate, and ethyl-4-dimethylamine benzoate.
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| CN202110666389.3A CN113249039A (en) | 2021-06-16 | 2021-06-16 | Optical adhesive |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110666389.3A CN113249039A (en) | 2021-06-16 | 2021-06-16 | Optical adhesive |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114035361A (en) * | 2021-11-11 | 2022-02-11 | 东莞市光志光电有限公司 | Brightness enhancement film with high brightness, scratch resistance and ball falling resistance |
| CN117143558A (en) * | 2023-10-26 | 2023-12-01 | 信泰永合(烟台)新材料有限公司 | High-specific gravity high-weather-resistance ultraviolet deep-curing adhesive and preparation method thereof |
| CN117447921A (en) * | 2023-10-26 | 2024-01-26 | 东莞市诺尔斯有机硅科技有限公司 | High refractive index optical organic glue composition and preparation method thereof |
-
2021
- 2021-06-16 CN CN202110666389.3A patent/CN113249039A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114035361A (en) * | 2021-11-11 | 2022-02-11 | 东莞市光志光电有限公司 | Brightness enhancement film with high brightness, scratch resistance and ball falling resistance |
| CN117143558A (en) * | 2023-10-26 | 2023-12-01 | 信泰永合(烟台)新材料有限公司 | High-specific gravity high-weather-resistance ultraviolet deep-curing adhesive and preparation method thereof |
| CN117143558B (en) * | 2023-10-26 | 2023-12-26 | 信泰永合(烟台)新材料有限公司 | High-specific gravity high-weather-resistance ultraviolet deep-curing adhesive and preparation method thereof |
| CN117447921A (en) * | 2023-10-26 | 2024-01-26 | 东莞市诺尔斯有机硅科技有限公司 | High refractive index optical organic glue composition and preparation method thereof |
| CN117447921B (en) * | 2023-10-26 | 2024-05-21 | 东莞市诺尔斯有机硅科技有限公司 | High refractive index optical organic glue composition and preparation method thereof |
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