CN111647136B - Resin packaging material and preparation method of QLED device - Google Patents

Resin packaging material and preparation method of QLED device Download PDF

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Publication number
CN111647136B
CN111647136B CN202010571703.5A CN202010571703A CN111647136B CN 111647136 B CN111647136 B CN 111647136B CN 202010571703 A CN202010571703 A CN 202010571703A CN 111647136 B CN111647136 B CN 111647136B
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reaction
acid
epoxy
resin
packaging material
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CN111647136A (en
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完亮亮
龙能文
骆意勇
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Hefei Funa Technology Co ltd
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Hefei Funa Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints

Abstract

The application provides a resin packaging material and a preparation method of a QLED device, and belongs to the field of packaging materials. The preparation method of the resin packaging material comprises the following steps: carrying out modification treatment on epoxy resin by adopting fluorinated substances to obtain a fluorine modified system; carrying out a first reaction on the fluorine modified system and dimer acid at the temperature of 85-95 ℃ to enable part of epoxy groups of the fluorine modified system to participate in the reaction, so as to obtain an epoxy intermediate system; and (3) carrying out a second reaction on the epoxy intermediate system and acrylic acid at the temperature of 100-110 ℃. The preparation method of the QLED device comprises the step of adopting the preparation method of the resin packaging material to prepare the resin packaging material. The prepared resin packaging material has good water-oxygen isolation effect and toughness, has good protection effect on the QLED device, and can effectively prolong the service life of the QLED device.

Description

Resin packaging material and preparation method of QLED device
Technical Field
The application relates to the field of packaging materials, in particular to a resin packaging material and a preparation method of a QLED device.
Background
The light emitting life of QLED (Quantum Dot Light Emitting Diodes) devices is drastically reduced by the influence of the ambient water oxygen, and thus the packaging of QLED devices is particularly important. In the prior art, the QLED device is generally packaged by adopting the UV resin, but the water-oxygen isolation effect of the UV resin can not well meet the use requirement, so that the service life of the QLED device is difficult to reach the performance requirement.
Disclosure of Invention
The application aims to provide a resin packaging material and a preparation method of a QLED device, wherein the prepared resin packaging material has good water-oxygen isolation effect and toughness, has good protection effect on the QLED device, and can effectively prolong the service life of the QLED device.
Embodiments of the present application are implemented as follows:
in a first aspect, an embodiment of the present application provides a method for preparing a resin encapsulation material, including:
carrying out modification treatment on epoxy resin by adopting fluorinated substances to obtain a fluorine modified system;
carrying out a first reaction on the fluorine modified system and dimer acid at the temperature of 85-95 ℃ to enable part of epoxy groups of the fluorine modified system to participate in the reaction, so as to obtain an epoxy intermediate system;
and (3) carrying out a second reaction on the epoxy intermediate system and acrylic acid at the temperature of 100-110 ℃.
In a second aspect, an embodiment of the present application provides a method for manufacturing a QLED device, including: the resin encapsulating material was prepared using the preparation method as provided in the example of the first aspect.
The preparation method of the resin packaging material and the QLED device provided by the embodiment of the application has the beneficial effects that:
the epoxy resin is modified by adopting a fluorinated substance, and the fluorinated substance has excellent chemical corrosion resistance, weather resistance and water and oxygen isolation effect, so that the hydrophobicity of the epoxy resin can be improved, and the prepared resin packaging material has good water and oxygen isolation effect. Meanwhile, the fluorinated substance has better self-cleaning property and high light transmittance, and can better meet the performance requirements of the packaging material.
The inventor researches that the toughness of the epoxy resin is smaller, and the thermal expansion coefficients of different materials in the QLED device are inconsistent, so that the stress generated between functional layers is difficult to release, and the black spot problem is easy to generate, thereby leading to the failure of the device.
The fluorine modified system and the dimer acid are reacted, and as the dimer acid contains a chemically inert long alkane chain and alicyclic structure, the nonpolar alkane and alicyclic in the dimer acid are introduced into a crosslinking system, so that the toughness of the fluorine modified epoxy system can be increased, and the prepared packaging material can better release the stress generated between functional layers. Meanwhile, the long alkyl side chain and alicyclic structure in the dimer acid have hydrophobicity, so that the equilibrium water absorption rate of the fluorine modified epoxy system can be reduced, the diffusion coefficient of water molecules in the fluorine modified epoxy system is obviously reduced, and the water-oxygen isolation effect of the packaging material is obviously improved. Moreover, the dimer acid is low in price, renewable and biodegradable, so that the packaging material is low in cost and good in environmental protection.
Dimer acid can better react with epoxy groups at the temperature of 85-95 ℃ to generate an intermediate, and then the intermediate can better react with epoxy groups at the temperature of 100-110 ℃; acrylic acid can react well with epoxy groups at 100-110 ℃. In the reaction process, dimer acid is firstly subjected to a first reaction with part of epoxy groups in the system at the temperature of 85-95 ℃, and then the system is subjected to a reaction with acrylic acid at the temperature of 100-110 ℃, so that both dimer acid and acrylic acid can be controllably reacted with epoxy groups in the system, and the reaction efficiency is high.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the present application, "and/or" such as "scheme a and/or scheme B" means that the solution may be the solution a alone, the solution B alone, or the solution a plus the solution B alone.
The preparation method of the resin packaging material and the QLED device in the embodiment of the application is specifically described below.
In a first aspect, an embodiment of the present application provides a method for preparing a resin encapsulation material, including:
s1, modifying epoxy resin by adopting a fluorinated substance to obtain a fluorine modified system.
The fluorinated substance has excellent chemical corrosion resistance, weather resistance and water and oil repellency, and can improve the hydrophobicity of the epoxy resin, so that the prepared resin packaging material has good water and oxygen isolation effect. Meanwhile, the fluorinated substance has better self-cleaning property and high light transmittance, and can better meet the performance requirements of the packaging material.
It will be appreciated that in embodiments of the present application, the fluorinated material may be chemically treated or physically treated to the epoxy. The kind of the fluorinated substance is not limited either, and may be selected according to the modification treatment method.
Illustratively, the fluorinated material is a fluoropolymer having a small radius of fluorine atoms, extremely strong electronegativity and low polarizability, and the bond energy of the c—f bond is high, and the fluoropolymer has excellent chemical resistance, weather resistance, and water and oil repellency.
In some exemplary embodiments, the modification treatment includes graft copolymerizing the epoxy resin with a fluorinated material. Alternatively, the fluorinated substance is hexafluorobutyl methacrylate, and the research shows that when the fluorinated substance is modified in a graft copolymerization mode, the reaction controllability of the fluorinated substance and the epoxy resin is good, and the improvement effect on the resin after the modification is good.
Exemplary, a graft copolymerization method of hexafluorobutyl methacrylate with an epoxy resin includes: in a reflux reaction vessel with a stirrer, the epoxy resin is dissolved in butyl acetate and stirred to a temperature of 100-110 ℃, for example to 100 ℃, so that the epoxy resin is fully dissolved. Maintaining a heating temperature, mixing and dissolving hexafluorobutyl methacrylate, an initiator and a cosolvent, wherein the initiator is selected from one or at least two of dibenzoyl peroxide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzophenone and 1-hydroxycyclohexyl phenyl ketone, and is 2-hydroxy-2-methyl-1-phenyl-1-acetone; the cosolvent is methyl methacrylate. Then, the mixture is dropped into a reflux reaction vessel, for example, using a constant pressure hopper at a dropping speed of 8 to 10 drops/min, and the volume of each drop is about 20. Mu.L in the embodiment of the present application. And (3) continuing the reflux reaction for 0.8-1.2h after the dripping is finished, for example, continuing the reflux reaction for 1h, and finishing the modification treatment to obtain a fluorine modified system containing fluorine modified resin.
In other exemplary embodiments, the modification treatment comprises mixing the epoxy resin with a fluorinated material, optionally at least one of polytetrafluoroethylene, fluorinated polyethylene and fluorocarbon wax, for example, any of them, and it has been found that the fluorinated material has good dispersibility with the epoxy resin and good improvement effect on the resin after the modification when the modification treatment is performed in a mixed manner.
S2, carrying out a first reaction on the fluorine modified system and the dimer acid at the temperature of 85-95 ℃ to enable part of epoxy groups of the fluorine modified system to participate in the reaction, so as to obtain an epoxy intermediate system.
S3, carrying out a second reaction on the epoxy intermediate system and acrylic acid at the temperature of 100-110 ℃.
Because the dimer acid contains a long alkane chain and alicyclic structure which are chemically inert, the nonpolar alkane and alicyclic in the dimer acid are introduced into a crosslinking system, so that the toughness of a fluorine modified epoxy system can be increased, the prepared packaging material can better release the stress generated between functional layers, and the problem of black spots can be effectively avoided, so that the device is invalid. Meanwhile, the long alkyl side chain and alicyclic structure in the dimer acid have hydrophobicity, so that the equilibrium water absorption rate of the fluorine modified epoxy system can be reduced, the diffusion coefficient of water molecules in the fluorine modified epoxy system is obviously reduced, and the water-oxygen isolation effect of the packaging material is obviously improved. Moreover, the dimer acid is low in price, renewable and biodegradable, so that the packaging material is low in cost and good in environmental protection.
It was found that dimer acid can react well with epoxy groups at 85-95 ℃ to form an intermediate, then the intermediate can react well with epoxy groups at 100-110 ℃, and acrylic acid can react well with epoxy groups at 100-110 ℃. In the embodiment of the application, the dimer acid is firstly subjected to a first reaction with part of epoxy groups in the system at the temperature of 85-95 ℃, and then the system is subjected to a reaction with the acrylic acid at the temperature of 100-110 ℃, so that the dimer acid and the acrylic acid can be controllably reacted with the epoxy groups in the system, and the reaction efficiency is high.
Illustratively, the temperature conditions of the first reaction are, for example, but not limited to, a range between any one or any two of 85 ℃, 90 ℃, and 95 ℃; the temperature conditions of the second reaction are, for example, but not limited to, a range between any one or any two of 100 ℃, 105 ℃ and 110 ℃.
In some possible embodiments, between the first reaction and the second reaction, further comprising: mixing the epoxy intermediate system and acrylic acid at 85-95 ℃ for 40-80 min to ensure that the system is fully and uniformly mixed, and preventing the generated resin components from being uneven to influence the encapsulation effect of the device; illustratively, the mixing temperature is maintained at the same temperature conditions as the first reaction for a time such as, but not limited to, a range between any one or any two of 40min, 50min, 60min, 70min, and 80 min. Namely, in the reaction system of the epoxy intermediate system and the acrylic acid, the mixture is firstly mixed for 40 to 80 minutes at the temperature of between 85 and 95 ℃, and then the second reaction is carried out at the temperature of between 100 and 110 ℃.
Regarding the reaction of the fluorine modification system and dimer acid:
in some possible embodiments, the first reaction is performed in the presence of a first catalyst, and the dimer acid contains a chemically inert long alkane chain and alicyclic structure, so that the reaction efficiency of the dimer acid and the fluorine modification system is improved by using the first catalyst for catalysis.
Optionally, the first catalyst is selected from at least one of N, N-dimethylbenzylamine, tetrabutylammonium bromide, triphenylphosphine and triethylamine. The research shows that the N, N-dimethylbenzylamine has the optimal catalytic effect, and then tetrabutylammonium bromide, triphenylphosphine and then triethylamine are adopted.
Illustratively, when the fluorine modified system reacts with the dimer acid, the dimer acid and the catalyst are mixed and then added into the fluorine modified system in a dropwise manner to participate in the reaction.
Further, in the first reaction, the acid value of the system is detected every 12-18min, for example every 15min, and the first reaction is ended when the acid value of the system is less than 3.5mg KOH/g, so that the dimer acid is ensured to fully participate in the reaction.
Regarding the reaction of the oxygen intermediate system with acrylic acid:
in some possible embodiments, the epoxy intermediate system and acrylic acid are reacted in the presence of a co-solvent, a second catalyst, and a polymerization inhibitor, ensuring that the reaction proceeds quickly and controllably. Optionally, the cosolvent is methyl methacrylate; the second catalyst is p-toluenesulfonic acid; the polymerization inhibitor is hydroquinone.
Illustratively, when the epoxy intermediate system is reacted with acrylic acid, a cosolvent, a second catalyst, and a polymerization inhibitor are added dropwise to the epoxy intermediate system to effect a reaction. The dropping operation is to mix the raw materials and then to drop the raw materials by adopting a constant pressure funnel, and the dropping speed is 8-10 drops/s, so that the controllability of the reaction is better.
Further, in the second reaction, the acid value of the system is detected every 25 to 35 minutes, for example, every 30 minutes, and the second reaction is ended when the acid value of the system is reduced to a preset value. The preset value is the theoretical acid value.
The acid value is the number of mg of KOH consumed to neutralize the acidic substance in 1g of the specimen. When the acid ester is determined, accurately weighing 0.5-1.0g of a sample to be measured in a 250ml conical flask, adding 20ml of absolute ethyl alcohol or acetone to completely dissolve the sample, dripping 2-4 drops of phenolphthalein indicator, and titrating with about 0.1mol/L KOH-ethanol standard solution until the sample is pink and does not fade for 30s, thus obtaining the titration end point. It is understood that in the examples of the present application, the theoretical acid value refers to a theoretical value of the acid value of the solution assuming complete reaction of the raw materials.
The research shows that the epoxy resin has the problem of easy yellowing in use, and the problem of resin yellowing can be effectively improved by adding the itaconic acid into the reaction system provided by the embodiment of the application. In addition, the itaconic acid can improve the water solubility of the resin, so that the resin has better service performance.
In some possible embodiments, the epoxy intermediate system and acrylic acid are reacted in the presence of itaconic acid. Itaconic acid and epoxy groups are added into the system to react, so that the problem of yellowing of the resin is effectively solved. The study also shows that itaconic acid can well react with epoxy groups at the temperature of 100-110 ℃, and itaconic acid is added in the reaction of an epoxy intermediate system and acrylic acid for reaction, so that the operation is convenient.
Illustratively, itaconic acid is added to the epoxy intermediate system prior to the acrylic acid being added dropwise to the epoxy intermediate system as it participates in the reaction of the epoxy intermediate system and acrylic acid.
Alternatively, the molar ratio of epoxy resin to itaconic acid is in the range of 10:3.5 to 4.5, such as, but not limited to, any one or between any two of 10:3.5, 10:4 and 10:4.5.
In embodiments where itaconic acid is added, the molar ratio of epoxy resin to dimer acid is optionally in the range of 10:1.5 to 2.5, such as, but not limited to, any one or between any two of 10:1.5, 10:2 and 10:2.5; the molar ratio of epoxy resin to acrylic is 10:3.5 to 4.5, such as, but not limited to, a range between any one or any two of 10:3.5, 10:4, and 10:4.5. The molar ratio of the epoxy resin to the dimer acid to the acrylic acid to the itaconic acid is 10:1.5-2.5:3.5-4.5:3.5-4.5 in sequence, for example, 10:2:4:4, and the amount of the groups introduced by the dimer acid, the acrylic acid and the itaconic acid is proper, so that the resin packaging material has better comprehensive performance.
Further, in embodiments where itaconic acid is not added, the molar ratio of epoxy resin to dimer acid is optionally in the range of 10:1.5 to 2.5, such as, but not limited to, any one or between any two of 10:1.5, 10:2 and 10:2.5; the molar ratio of epoxy resin to acrylic is 10:3.5 to 4.5, such as, but not limited to, a range between any one or any two of 10:3.5, 10:4, and 10:4.5. Illustratively, the molar ratio of epoxy resin, dimer acid to acrylic acid is 10:2:4 in order.
After the second reaction, in some possible embodiments, further comprising: cooling the system to 55-65 ℃, for example to 55 ℃, 60 ℃ and 65 ℃ or any range between any two; the system is then neutralized and the pH of the system is adjusted to a value of 6 to 7, for example to a range between any one or any two of 6, 6.5 and 7.
Further, after neutralization, distilled water is added, and the mixture is continuously stirred to be uniformly distributed, so that the aqueous resin packaging material is obtained, and the discharged material is stored in a closed container for standby.
In a second aspect, an embodiment of the present application provides a method for manufacturing a QLED device, including: the resin packaging material is prepared by adopting the preparation method of the resin packaging material provided by the embodiment of the first aspect. The prepared epoxy resin has good water-oxygen isolation effect and toughness, has good protection effect on the QLED device, and can effectively prolong the service life of the QLED device.
The QLED device is an exemplary front-end bottom emission structure, and includes a body structure and a packaging structure for packaging the body structure, where the material of the packaging structure is the resin packaging material prepared by the method for preparing a resin packaging material provided by the embodiment of the first aspect, and the body structure includes a transparent anode substrate, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, a transition layer, and a metal cathode, which are sequentially arranged. Optionally, the electron transport layer is a nano metal oxide deposited layer structure, the transition layer is a nano metal oxide deposited particle structure, and the reflection of the cathode to visible light is not less than 98%.
The preparation method of the QLED device with the front bottom emission structure comprises the following steps:
on the transparent anode substrate, a hole injection layer is deposited.
On the hole injection layer, a hole transport layer is deposited.
And depositing a quantum dot light-emitting layer on the hole transport layer.
And depositing a nano metal oxide electron transport layer on the quantum dot light-emitting layer.
And depositing a nano metal oxide particle transition layer on the electron transport layer.
A metal cathode is deposited on the transition layer.
The resin packaging material is prepared for packaging by adopting the preparation method of the resin packaging material provided by the embodiment of the first aspect.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
A preparation method of a resin packaging material comprises the following steps:
s1, adding epoxy resin and butyl acetate into a four-neck flask provided with a stirring paddle, a constant-pressure funnel, a condenser tube and a thermometer, stirring and heating to 110 ℃ to dissolve the epoxy resin. The mixed solution of hexafluorobutyl methacrylate, 2-hydroxy-2-methyl-1-phenyl-1-propanone and methyl methacrylate is added into a four-necked flask through a constant pressure funnel at a speed of 8-10 drops/min. And after the dripping is finished, continuing to reflux and react for 1h to obtain a fluorine modified system.
S2, cooling the system to 90 ℃, and dropwise adding the mixed solution of dimer acid and N, N-dimethylbenzylamine into a four-neck flask through a constant pressure funnel, wherein the acid value is measured every 15min until the acid value of the system is reduced by less than 3.5mg KOH/g.
S3, adding itaconic acid into the four-necked flask, dripping a mixed solution of acrylic acid, methyl methacrylate, p-toluenesulfonic acid and hydroquinone into the four-necked flask through a constant pressure funnel at a speed of 2-3 drops/s, mixing for 1h under the condition of keeping at 90 ℃, then continuing to react at the temperature of 105 ℃, and measuring the acid value once every 30min until the acid value of the system is reduced to the theoretical acid value.
S4, cooling the system, adjusting the pH value of the system to 6.5 when the temperature of the system is reduced to 60 ℃, and then adding distilled water in proportion and uniformly stirring to obtain the water-based resin packaging material.
Wherein the molar ratio of the epoxy resin to the dimer acid to the acrylic acid to the itaconic acid is 10:2:4:4 in sequence.
Example 2
A preparation method of a resin packaging material comprises the following steps:
s1, adding epoxy resin and butyl acetate into a four-neck flask provided with a stirring paddle, a constant-pressure funnel, a condenser tube and a thermometer, stirring and heating to 110 ℃ to dissolve the epoxy resin. The mixed solution of hexafluorobutyl methacrylate, 2-hydroxy-2-methyl-1-phenyl-1-propanone and methyl methacrylate is added into a four-necked flask through a constant pressure funnel at a speed of 8-10 drops/min. And after the dripping is finished, continuing to reflux and react for 1h to obtain a fluorine modified system.
S2, cooling the system to 85 ℃, and dropwise adding the mixed solution of dimer acid and N, N-dimethylbenzylamine into a four-neck flask through a constant pressure funnel, wherein the acid value is measured every 15min until the acid value of the system is reduced by less than 3.5mg KOH/g.
S3, adding itaconic acid into the four-necked flask, dripping a mixed solution of acrylic acid, methyl methacrylate, p-toluenesulfonic acid and hydroquinone into the four-necked flask through a constant pressure funnel at a speed of 2-3 drops/s, mixing for 1h under the condition of keeping at 85 ℃, then continuing to react at the temperature of 100 ℃, and measuring the acid value once every 30min until the acid value of the system is reduced to the theoretical acid value.
S4, cooling the system, adjusting the pH value of the system to 6.5 when the temperature of the system is reduced to 60 ℃, and then adding distilled water in proportion and uniformly stirring to obtain the water-based resin packaging material.
Wherein the molar ratio of the epoxy resin to the dimer acid to the acrylic acid to the itaconic acid is 10:2:4:4 in sequence.
Example 3
A preparation method of a resin packaging material comprises the following steps:
s1, adding epoxy resin and butyl acetate into a four-neck flask provided with a stirring paddle, a constant-pressure funnel, a condenser tube and a thermometer, stirring and heating to 110 ℃ to dissolve the epoxy resin. The mixed solution of hexafluorobutyl methacrylate, 2-hydroxy-2-methyl-1-phenyl-1-propanone and methyl methacrylate is added into a four-necked flask through a constant pressure funnel at a speed of 8-10 drops/min. And after the dripping is finished, continuing to reflux and react for 1h to obtain a fluorine modified system.
S2, cooling the system to 95 ℃, and dropwise adding the mixed solution of dimer acid and N, N-dimethylbenzylamine into a four-neck flask through a constant pressure funnel, wherein the acid value is measured every 15min until the acid value of the system is reduced by less than 3.5mg KOH/g.
S3, adding itaconic acid into the four-necked flask, dripping a mixed solution of acrylic acid, methyl methacrylate, p-toluenesulfonic acid and hydroquinone into the four-necked flask through a constant pressure funnel at a speed of 2-3 drops/s, mixing for 1h under the condition of 95 ℃, then continuing to react at the temperature of 110 ℃, and measuring the acid value once every 30min until the acid value of the system is reduced to the theoretical acid value.
S4, cooling the system, adjusting the pH value of the system to 6.5 when the temperature of the system is reduced to 60 ℃, and then adding distilled water in proportion and uniformly stirring to obtain the water-based resin packaging material.
Wherein, the molar ratio of the epoxy resin to the hexafluorobutyl methacrylate is 4:1; the molar ratio of the epoxy resin, the dimer acid, the acrylic acid and the itaconic acid is 10:2:4:4 in sequence.
Example 4
A method for producing a resin encapsulating material, which differs from example 1 only in that:
the molar ratio of the epoxy resin, the dimer acid, the acrylic acid and the itaconic acid is 10:1.5:4:4.5 in sequence.
Example 5
A method for producing a resin encapsulating material, which differs from example 1 only in that:
the molar ratio of the epoxy resin, the dimer acid, the acrylic acid and the itaconic acid is 10:1.5:4.5:4 in sequence.
Example 6
A method for producing a resin encapsulating material, which differs from example 1 only in that:
the molar ratio of the epoxy resin, the dimer acid, the acrylic acid and the itaconic acid is 10:2.5:4:3.5 in sequence.
Example 7
A method for producing a resin encapsulating material, which differs from example 1 only in that:
the molar ratio of epoxy resin, dimer acid, acrylic acid and itaconic acid is 10:2.5:3.5:4 in sequence.
Example 8
A method for producing a resin encapsulating material, which differs from example 1 only in that:
in the step S3, itaconic acid is not added, and the molar ratio of epoxy resin to dimer acid to acrylic acid is 10:2:4 in sequence.
Example 9
A method for producing a resin encapsulating material, which differs from example 1 only in that:
in the step S1, the fluorine modified system is prepared by mixing epoxy resin and polytetrafluoroethylene, wherein the molar ratio of the epoxy resin to the polytetrafluoroethylene is 5:1.
Example 10
A preparation method of a positive QLED device comprises the following steps:
on the transparent anode substrate, a hole injection layer is deposited.
On the hole injection layer, a hole transport layer is deposited.
And depositing a quantum dot light-emitting layer on the hole transport layer.
And depositing a nano metal oxide electron transport layer on the quantum dot light-emitting layer.
And depositing a nano metal oxide particle transition layer on the electron transport layer.
And depositing a metal cathode on the transition layer, wherein the reflection of the cathode to visible light is not less than 98%.
Encapsulation was performed using the resin encapsulation material prepared in example 1: the dosage of resin added dropwise on the surface of the matrix is 1g/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Curing with UV lamp with intensity of 300mJ/cm 2 The time is 60s.
Example 11
A method for manufacturing a front-end QLED device, which is different from embodiment 10 in that:
encapsulation was performed using the resin encapsulation material prepared in example 8.
Example 12
A method for manufacturing a front-end QLED device, which is different from embodiment 10 in that:
encapsulation was performed using the resin encapsulation material prepared in example 9.
Comparative example 1
A method for manufacturing a front-end QLED device, which is different from embodiment 10 in that:
encapsulation is carried out by adopting unmodified UV epoxy acrylic resin.
Test examples
The performance of the front-end QLED devices obtained in examples 10 to 12 and comparative example 1 was examined, wherein the service life was 100cd/cm 2 Lifetime of the red QD-LED. The test results are shown in Table 1.
TABLE 1 Performance of front-mounted QLED devices
Example 10 Example 11 Example 12 Comparative example 1
Water contact angle degree 90 85 78 65
Water absorption percentage% 3 5 9 12
Flexibility mm 2 5 10 15
Impact resistance kg cm 50 45 8 10
Color of Transparent and transparent Light yellow Light yellow Light yellow
Life h 90000 85000 82500 75000
As can be seen from Table 1, the resin packaging material prepared by the preparation method of the resin packaging material provided by the embodiment of the application has good water-oxygen isolation effect and toughness, and has good protection effect on the QLED device when being used for packaging the QLED device, and the service life of the QLED device is obviously prolonged.
The embodiments described above are some, but not all embodiments of the application. The detailed description of the embodiments of the application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.

Claims (8)

1. A method for preparing a resin encapsulation material, comprising:
carrying out modification treatment on epoxy resin by adopting fluorinated substances to obtain a fluorine modified system; wherein the fluorinated material is hexafluorobutyl methacrylate;
carrying out a first reaction on the fluorine modified system and dimer acid at the temperature of 85-95 ℃ to enable part of epoxy groups of the fluorine modified system to participate in the reaction, so as to obtain an epoxy intermediate system;
mixing the epoxy intermediate system and the acrylic acid for 40-80 min at the temperature of 85-95 ℃; then carrying out a second reaction at the temperature of 100-110 ℃; reacting the epoxy intermediate system with the acrylic acid in the presence of itaconic acid;
wherein the molar ratio of the epoxy resin to the itaconic acid is 10:3.5-4.5; the molar ratio of the epoxy resin to the dimer acid is 10:1.5-2.5; the molar ratio of the epoxy resin to the acrylic acid is 10:3.5-4.5.
2. The method according to claim 1, wherein in the first reaction, the acid value of the system is detected every 12 to 18 minutes, and the first reaction is ended when the acid value of the system is less than 3.5mg KOH/g;
and/or, the first reaction is carried out in the presence of a first catalyst.
3. The process according to claim 1 or 2, wherein the epoxy intermediate system and the acrylic acid are reacted in the presence of a co-solvent, a second catalyst and a polymerization inhibitor.
4. The method according to claim 3, wherein the acrylic acid, the cosolvent, the second catalyst and the polymerization inhibitor are added dropwise to the epoxy intermediate system for reaction when the epoxy intermediate system and the acrylic acid are reacted.
5. The method according to claim 3, wherein in the second reaction, the acid value of the system is detected every 25 to 35 minutes, and the second reaction is terminated when the acid value of the system is lowered to a predetermined value.
6. The production method according to claim 1 or 2, wherein the modification treatment comprises graft copolymerizing the epoxy resin with the fluorinated substance.
7. The method according to claim 1 or 2, wherein the second reaction further comprises: and cooling the system to 55-65 ℃, and then adjusting the pH value of the system to 6-7.
8. A method for manufacturing a QLED device, wherein the resin encapsulation material is manufactured by using the manufacturing method according to any one of claims 1 to 7.
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CN104448712A (en) * 2014-12-24 2015-03-25 中科院广州化学有限公司 Organic fluorine modified epoxy LED packaging material and preparation method thereof
CN105418419A (en) * 2015-11-02 2016-03-23 安庆市虹泰新材料有限责任公司 Dimer acid modified epoxy resin and preparation method therefor
WO2016170893A1 (en) * 2015-04-20 2016-10-27 Jnc株式会社 Curable resin composition and electronic devices such as organic electroluminescence element using cured product thereof
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CN104448712A (en) * 2014-12-24 2015-03-25 中科院广州化学有限公司 Organic fluorine modified epoxy LED packaging material and preparation method thereof
WO2016170893A1 (en) * 2015-04-20 2016-10-27 Jnc株式会社 Curable resin composition and electronic devices such as organic electroluminescence element using cured product thereof
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