CN116333671A - LED packaging adhesive capable of deep UV curing and preparation method and application thereof - Google Patents

LED packaging adhesive capable of deep UV curing and preparation method and application thereof Download PDF

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Publication number
CN116333671A
CN116333671A CN202310190794.1A CN202310190794A CN116333671A CN 116333671 A CN116333671 A CN 116333671A CN 202310190794 A CN202310190794 A CN 202310190794A CN 116333671 A CN116333671 A CN 116333671A
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parts
packaging adhesive
stirring
weight
acrylic ester
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黄计锋
闻明
徐华斌
史小珍
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Shenzhen Sunyes New Material Co ltd
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Shenzhen Sunyes New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention belongs to the technical field of packaging adhesives, and particularly relates to a deep UV-curable LED packaging adhesive, and a preparation method and application thereof. An encapsulation adhesive comprises polyurethane acrylic ester, a reactive diluent and a photoinitiator; the viscosity of the polyurethane acrylic ester at 25 ℃ is 5000-8000 mPa.s; the addition ratio of the polyurethane acrylic ester, the reactive diluent and the photoinitiator is 100: (18-55): (3-12), the packaging adhesive also comprises a defoaming agent and/or a polymerization inhibitor. The packaging adhesive comprises, by weight, 100 parts of polyurethane acrylic ester, 18-55 parts of reactive diluent, 3-12 parts of photoinitiator, 0.3-1.7 parts of defoamer and 0.3-1.7 parts of polymerization inhibitor. The packaging adhesive provided by the invention has the advantages that the curing depth is deeper, the thickness of a construction adhesive layer can be increased, the light transmittance, the refractive index and the mechanical property are good, and the sealing and luminous performance requirements of an LED can be met.

Description

LED packaging adhesive capable of deep UV curing and preparation method and application thereof
Technical Field
The invention belongs to the technical field of packaging adhesives, and particularly relates to a deep UV-curable LED packaging adhesive, and a preparation method and application thereof.
Background
In recent years, LEDs, which are a semiconductor light emitting device, are rapidly being widely used in the fields of lighting, backlight, display screens, etc., due to their advantages of energy saving, long life, environmental protection, high light efficiency, etc. In order to meet the luminous performance requirement of an LED, the packaging adhesive used in the packaging process of the LED also provides higher and higher requirements, and generally needs to meet the requirements of rapid curing and deeper curing depth, so that the thickness of a construction adhesive layer can be increased to better ensure sealing and protection effects.
At present, most of LED packaging adhesives on the market adopt epoxy resin and organic silicon materials as main raw materials, the curing mode is heating curing, higher temperature and longer time are needed, for example, OE-8500 curing conditions are 150 ℃ for 1 hour, OE-6635 curing conditions are 150 ℃ for 2 hours, the production efficiency is lower, the industrial application is not facilitated, the curing depth of the packaging adhesive is insufficient, and good sealing and protecting effects cannot be guaranteed. In addition, the viscosity of the packaging adhesive is correspondingly higher, so that the packaging adhesive is not easy to cure and the curing depth is insufficient, and good sealing and protecting effects cannot be ensured. Meanwhile, the refractive index and the light transmittance of the packaging adhesive are low, the light transmittance is only 80% -92%, and the luminous performance of the LED cannot be fully utilized.
Therefore, it is needed to provide an LED packaging adhesive, which has good light transmittance and refractive index, deep curing depth, and good mechanical properties, and can meet the requirements of sealing and light emitting performance of the LED.
Disclosure of Invention
The present invention is directed to solving one or more of the problems of the prior art and providing at least one of a beneficial choice or creation of conditions. The LED packaging adhesive capable of being deeply cured is good in light transmittance and refractive index, deep in curing depth and good in mechanical property, and can fully meet the requirements of sealing and luminous performance of an LED.
The invention is characterized in that: according to the invention, the polyurethane acrylic ester with the viscosity of 5000-8000 mPa.s at 25 ℃ is adopted, so that the prepared packaging adhesive has proper viscosity, curing of the packaging adhesive is facilitated, the curing depth of more than 5mm is obtained, in addition, the polyurethane acrylic ester, the reactive diluent and the photoinitiator are combined to act together, and the packaging adhesive can be quickly cured and the curing depth can exceed 5mm under the action of UV (ultraviolet) according to a certain adding proportion, so that the thickness of a construction adhesive layer can be increased, good sealing and protecting effects are ensured, meanwhile, the refractive index is good, the light utilization rate is improved, the mechanical property is good, the light transmittance is high, and the sealing and luminous performance requirements of an LED can be fully met.
Accordingly, a first aspect of the present invention provides a deep UV curable LED encapsulation compound.
Specifically, an LED packaging adhesive, the LED packaging adhesive includes: polyurethane acrylic ester, reactive diluent and photoinitiator;
the viscosity of the polyurethane acrylic ester at 25 ℃ is 5000-8000 mPa.s;
the content ratio of the polyurethane acrylic ester, the reactive diluent and the photoinitiator is 100: (18-55): (3-12).
Specifically, the viscosity of the polyurethane acrylic ester cannot be too high or too low, the viscosity is too high, so that the prepared packaging adhesive is large in viscosity, construction is not facilitated, curing time is prolonged, and meanwhile, the refractive index and light transmittance of the packaging adhesive are reduced; too low viscosity can affect the thickness and mechanical properties of the construction glue layer, thereby affecting the sealing and protecting effects of the packaging glue.
Specifically, polyurethane acrylic ester, reactive diluent and photoinitiator act together and are compounded according to a certain adding proportion, so that the packaging adhesive can be rapidly cured under the action of UV, the curing depth can exceed 5mm, the thickness of a construction adhesive layer can be increased, good sealing and protecting effects are ensured, meanwhile, the packaging adhesive has good refractive index, the light utilization rate can be improved, meanwhile, the mechanical property is good, the light transmittance is high, and the sealing and luminous performance requirements of an LED are fully met.
Preferably, the packaging adhesive comprises 100 parts of polyurethane acrylic ester, 18-55 parts of reactive diluent and 3-12 parts of photoinitiator in parts by weight.
Preferably, the packaging adhesive further comprises a defoaming agent and/or a polymerization inhibitor.
Preferably, the packaging adhesive comprises 100 parts by weight of polyurethane acrylic ester, 18-55 parts by weight of reactive diluent, 3-12 parts by weight of photoinitiator, 0.3-1.7 parts by weight of defoamer and 0.3-1.7 parts by weight of polymerization inhibitor.
Preferably, the packaging adhesive comprises 100 parts by weight of polyurethane acrylic ester, 20-50 parts by weight of reactive diluent, 5-10 parts by weight of photoinitiator, 0.5-1.5 parts by weight of defoamer and 0.5-1.5 parts by weight of polymerization inhibitor.
Preferably, the reactive diluent is at least one selected from isobornyl methacrylate, tetrahydrofuranyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate and neopentyl glycol diacrylate.
Preferably, the photoinitiator is selected from at least one of ethyl 2,4, 6-trimethylbenzoyl phosphonate, 2-diethoxy-1-phenylhexanone, alpha-hydroxyisobutyrophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, 1-hydroxycyclohexyl phenyl ketone.
Preferably, the defoamer is at least one selected from polydimethylsiloxane, fluorosilicone and ethylene glycol siloxane.
Preferably, the polymerization inhibitor is at least one selected from the group consisting of p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, and tris (N-nitroso-N-phenylhydroxylamine) aluminum salt.
The second aspect of the invention provides a preparation method of a deep UV-curable LED packaging adhesive.
Specifically, the preparation method comprises the following steps:
and mixing and stirring the raw material components under the vacuum condition to obtain the LED packaging adhesive.
Preferably, the vacuum degree of the vacuum condition is-0.085 to-0.1 MPa.
Further preferably, the vacuum degree of the vacuum condition is-0.095 to-0.1 MPa.
Preferably, the stirring speed is 90-330r/min, and the stirring time is 0.5-3h.
Further preferably, the stirring speed is 100-300r/min, and the stirring time is 1-2.5h.
Preferably, the preparation method specifically comprises the following steps:
(1) Adding polyurethane acrylic ester, an active diluent and a photoinitiator into a stirring kettle, and mixing and stirring under vacuum conditions to obtain a mixed solution;
(2) And (3) adding a defoaming agent and a polymerization inhibitor into the mixed solution obtained in the step (1), and mixing and stirring under a vacuum condition to obtain the deep UV-curable LED packaging adhesive.
Preferably, in the step (1) and the step (2), the vacuum degree of the vacuum condition is-0.085 to-0.1 MPa.
Further preferably, in step (1) and step (2), the vacuum degree of the vacuum condition is-0.095 to-0.1 MPa.
Preferably, in the step (1), the stirring speed is 90-330r/min, and the stirring time is 0.5-3h.
Further preferably, in the step (1), the stirring speed is 100-300r/min, and the stirring time is 1-2.5h.
Preferably, in the step (2), the stirring speed is 90-330r/min, and the stirring time is 0.5-3h.
Further preferably, in the step (2), the stirring speed is 100-300r/min, and the stirring time is 1-2.5h.
Preferably, the preparation method of the polyurethane acrylic ester comprises the following steps:
(1) Mixing diisocyanate and polyether glycol, adding a catalyst, heating and stirring to obtain a mixture;
(2) And (3) cooling the mixture obtained in the step (1), adding hydroxy methacrylate and p-phenol, and stirring to obtain the polyurethane acrylate.
Specifically, the existing polyurethane acrylate preparation method is generally that diisocyanate reacts with hydroxyl acrylate to generate acrylate and then reacts with glycol, and when the preparation method is adopted, the acrylate stays in a reaction kettle for a long time and is easy to be heated and polymerized, so that the viscosity of the polyurethane acrylate is influenced, and further the chromaticity and photopolymerization activity of the product are adversely influenced. When the polyurethane acrylic ester is prepared, diisocyanate and diol are firstly subjected to chain extension and then react with hydroxyl acrylate, so that the residence time of the hydroxyl acrylate in a kettle can be shortened, excessive polymerization and even gel caused by overlong heating time of the hydroxyl acrylate are avoided, the viscosity of the polyurethane acrylic ester can be reduced, the proper viscosity of the packaging adhesive is ensured, and the packaging adhesive has good curing depth, refractive index, light transmittance and mechanical property, and the sealing and luminous performance requirements of an LED are ensured.
Preferably, in step (1), the molar ratio of the diisocyanate to the polyether glycol is (1.9-2.1): (0.9-1.1).
Further preferably, in step (1), the molar ratio of the diisocyanate to the polyether glycol is 2:1.
preferably, in the step (1), the addition amount of the catalyst accounts for 0.04% -0.22% of the total weight of the diisocyanate and the polyether glycol.
Further preferably, in the step (1), the addition amount of the catalyst is 0.05% -0.2% of the total weight of the diisocyanate and the polyether glycol.
Preferably, in the step (1), the heating temperature of the heating and stirring is 55-105 ℃; the stirring speed of the heating and stirring is 90-330r/min, and the stirring time of the heating and stirring is 1.5-5.5h.
Further preferably, in the step (1), the heating temperature of the heating and stirring is 60-100 ℃; the stirring speed of the heating and stirring is 100-300r/min, and the stirring time of the heating and stirring is 2-5h.
Preferably, in the step (2), the temperature of the cooling is 40-55 ℃.
Further preferably, in the step (2), the temperature of the cooling is 45-50 ℃.
Preferably, in step (2), the molar ratio of the diisocyanate to the hydroxy methacrylate is (0.9-1.1): (0.9-1.1).
Further preferably, in the step (2), the molar ratio of the diisocyanate to the hydroxy methacrylate is 1:1.
preferably, in the step (2), the added amount of the p-phenol is 0.06-0.14% of the total weight of the diisocyanate, the polyether glycol, the catalyst and the hydroxy methacrylate.
Further preferably, in the step (2), the added amount of the p-phenol is 0.08 to 0.12% of the total weight of the diisocyanate, the polyether glycol, the catalyst and the hydroxy methacrylate.
Still more preferably, in the step (2), the p-phenol is added in an amount of 0.1% by weight based on the total weight of the diisocyanate, the polyether glycol, the catalyst and the hydroxy methacrylate.
Preferably, in the step (2), the stirring speed is 90-330r/min, and the stirring time is 1.5-5.5h.
Further preferably, in the step (2), the stirring speed is 100-300r/min, and the stirring time is 2-5h.
Preferably, the diisocyanate is at least one selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.
Further preferably, the diisocyanate is isophorone diisocyanate.
Preferably, the catalyst is at least one selected from dibutyl tin dilaurate, dioctyl tin dilaurate and dibutyl tin diacetate.
Preferably, the hydroxy methacrylate is at least one selected from the group consisting of hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The third aspect of the invention provides an application of the deep UV-curable LED packaging adhesive in the field of LED packaging.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
(1) According to the invention, the polyurethane acrylic ester with the viscosity of 5000-8000 mPa.s at 25 ℃ is adopted, so that the prepared packaging adhesive has proper viscosity, is beneficial to the curing of the packaging adhesive and has reasonable curing depth, in addition, the polyurethane acrylic ester, the reactive diluent and the photoinitiator are combined to act together, and the packaging adhesive can be quickly cured under the action of UV (ultraviolet) according to a certain adding proportion, the curing depth can reach more than 5mm, so that the thickness of a construction adhesive layer can be increased, good sealing and protecting effects are ensured, meanwhile, the packaging adhesive has good light transmittance, refractive index and mechanical property, the light transmittance can reach more than 95%, the refractive index can reach more than 1.5, and the luminous performance requirement of an LED can be fully met.
(2) The packaging adhesive provided by the invention can be quickly cured by combining with UV curing, and has high production efficiency.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The polyether glycol used in the examples and comparative examples of the present invention has at least one type selected from the group consisting of PEG100, PEG200, and PEG 300.
Example 1
The deep UV curable LED packaging adhesive comprises the following components in parts by weight:
100 parts of polyurethane acrylic ester, 20 parts of isobornyl methacrylate, 5 parts of ethyl 2,4, 6-trimethylbenzoyl phosphonate, 0.5 part of polydimethylsiloxane and 1 part of p-hydroxyanisole.
The preparation method of the polyurethane acrylic ester comprises the following steps:
(1) Adding 2mol of isophorone diisocyanate and 1mol of PEG100 into a reaction kettle, then adding 0.54g of dibutyltin dilaurate, stirring at 70 ℃ for 2.5h at a stirring speed of 100r/min to obtain a mixture;
(2) And (3) cooling the mixture obtained in the step (1) to 45 ℃, adding 2mol of hydroxyethyl methacrylate and 0.80g of p-phenol, and stirring at a speed of 100r/min for 2.5h to obtain the polyurethane acrylate.
A preparation method of deep UV curable LED packaging adhesive comprises the following steps:
(1) Adding 100 parts of urethane acrylate, 20 parts of isobornyl methacrylate and 5 parts of 2,4, 6-trimethylbenzoyl ethyl phosphonate into a stirring kettle, and stirring under the condition of the vacuum degree of-0.095 MPa at the stirring speed of 100r/min for 1h to obtain a mixed solution;
(2) Adding 0.5 part of polydimethylsiloxane and 1 part of p-hydroxyanisole into the mixed solution obtained in the step (1), and stirring under the condition of vacuum degree of-0.095 MPa, wherein the stirring speed is 100r/min, and the stirring time is 1.5h, so that the LED packaging adhesive capable of deep UV curing is obtained.
Example 2
The deep UV curable LED packaging adhesive comprises the following components in parts by weight: 100 parts of polyurethane acrylic ester, 30 parts of tetrahydrofuran acrylate, 7 parts of 2, 2-diethoxy-1-cyclohexanone, 1 part of polydimethylsiloxane and 1 part of p-hydroxyanisole.
The preparation method of the polyurethane acrylic ester comprises the following steps:
(1) Adding 2mol of isophorone diisocyanate and 1mol of PEG200 into a reaction kettle, then adding 0.64g of dioctyltin dilaurate, stirring at 70 ℃ for 3 hours at a stirring speed of 150r/min to obtain a mixture;
(2) And (3) cooling the mixture obtained in the step (1) to 50 ℃, adding 2mol of hydroxypropyl methacrylate and 0.93g of p-phenol, and stirring at a speed of 150r/min for 2.5h to obtain polyurethane acrylate.
A preparation method of deep UV curable LED packaging adhesive comprises the following steps:
(1) Adding 100 parts of polyurethane acrylic ester, 30 parts of tetrahydrofuran acrylate and 7 parts of 2, 2-diethoxy-1-cyclohexanone into a stirring kettle, and stirring under the condition of vacuum degree of-0.098 MPa at the stirring speed of 200r/min for 1.5h to obtain a mixed solution;
(2) Adding 1 part of polydimethylsiloxane and 1 part of para-hydroxyanisole into the mixed solution obtained in the step (1), stirring under the condition of vacuum degree of-0.098 MPa, wherein the stirring speed is 200r/min, and the stirring time is 1.5h, so as to obtain the deep UV-curable LED packaging adhesive
Example 3
The deep UV curable LED packaging adhesive comprises the following components in parts by weight: 100 parts of polyurethane acrylic ester, 40 parts of dipropylene glycol diacrylate, 7 parts of alpha-hydroxy isobutyryl benzene, 1.5 parts of fluorosilicone and 1 part of tris (N-nitroso-N-phenylhydroxylamine) aluminum salt.
The preparation method of the polyurethane acrylic ester comprises the following steps:
(1) Adding 2.1mol of isophorone diisocyanate and 1mol of PEG200 into a reaction kettle, then adding 1g of dioctyltin dilaurate, stirring at 75 ℃ for 3 hours at a stirring speed of 200r/min to obtain a mixture;
(2) And (3) cooling the mixture obtained in the step (1) to 48 ℃, adding 2.1mol of hydroxyethyl methacrylate and 0.74g of p-phenol, and stirring at the speed of 200r/min for 3.5h to obtain the polyurethane acrylate.
A preparation method of deep UV curable LED packaging adhesive comprises the following steps:
(1) Adding 100 parts of polyurethane acrylic ester, 40 parts of dipropylene glycol diacrylate and 7 parts of alpha-hydroxy isobutyryl benzene into a stirring kettle, stirring under the condition of vacuum degree of-0.096 MPa, wherein the stirring speed is 150r/min, and the stirring time is 2h, so as to obtain a mixed solution;
(2) Adding 1.5 parts of fluorosilicone and 1 part of tris (N-nitroso-N-phenylhydroxylamine) aluminum salt into the mixed solution obtained in the step (1), stirring under the condition of vacuum degree of-0.096 MPa, wherein the stirring speed is 200r/min, and the stirring time is 1.5h, so as to obtain the deep UV curable LED packaging adhesive.
Example 4
The deep UV curable LED packaging adhesive comprises the following components in parts by weight: 100 parts of urethane acrylate, 45 parts of tripropylene glycol diacrylate, 7 parts of alpha-hydroxy isobutyrophenone, 0.8 part of fluorosilicone and 1.2 parts of tris (N-nitroso-N-phenylhydroxylamine) aluminum salt.
The preparation method of the polyurethane acrylic ester comprises the following steps:
(1) Adding 2mol of isophorone diisocyanate and 0.9mol of PEG300 into a reaction kettle, then adding 0.86g of dibutyltin diacetate, stirring at the temperature of 75 ℃ at the stirring speed of 250r/min for 2h to obtain a mixture;
(2) And (3) cooling the mixture obtained in the step (1) to 50 ℃, adding 2mol of hydroxyethyl methacrylate and 1.67g of p-phenol, and stirring at a speed of 150r/min for 3 hours to obtain the polyurethane acrylate.
A preparation method of deep UV curable LED packaging adhesive comprises the following steps:
(1) Adding 100 parts of polyurethane acrylic ester, 45 parts of tripropylene glycol diacrylate and 7 parts of alpha-hydroxy isobutyryl benzene into a stirring kettle, stirring under the condition of vacuum degree of-0.1 MPa, wherein the stirring speed is 250r/min, and the stirring time is 1h, so as to obtain a mixed solution;
(2) Adding 0.8 part of fluorosilicone and 1.2 parts of tris (N-nitroso-N-phenylhydroxylamine) aluminum salt into the mixed solution obtained in the step (1), stirring at the vacuum degree of-0.1 MPa, wherein the stirring speed is 150r/min, and the stirring time is 2.5h, so as to obtain the deep UV curable LED packaging adhesive.
Example 5
The deep UV curable LED packaging adhesive comprises the following components in parts by weight: 100 parts of polyurethane acrylic ester, 40 parts of tripropylene glycol diacrylate, 8 parts of 1-hydroxycyclohexyl phenyl ketone, 1.5 parts of ethylene glycol siloxane and 1 part of 2, 6-di-tert-butyl-p-toluene phenol.
The preparation method of the polyurethane acrylic ester comprises the following steps:
(1) Adding 2mol of isophorone diisocyanate and 1mol of PEG200 into a reaction kettle, then adding 0.97g of dibutyltin diacetate, stirring at 95 ℃ for 4 hours at the speed of 250r/min to obtain a mixture;
(2) And (3) cooling the mixture obtained in the step (1) to 45 ℃, adding 2mol of hydroxypropyl methacrylate and 0.93g of p-phenol, and stirring at the speed of 200r/min for 4 hours to obtain the polyurethane acrylate.
A preparation method of deep UV curable LED packaging adhesive comprises the following steps:
(1) Adding 100 parts of polyurethane acrylic ester, 40 parts of tripropylene glycol diacrylate and 8 parts of 1-hydroxycyclohexyl phenyl ketone into a stirring kettle, stirring under the condition of vacuum degree of-0.095 MPa, wherein the stirring speed is 150r/min, and the stirring time is 2h, so as to obtain a mixed solution;
(2) Adding 1.5 parts of ethylene glycol siloxane and 1 part of 2, 6-di-tert-butyl-p-cresol into the mixed solution obtained in the step (1), stirring under the condition of vacuum degree of-0.095 MPa, wherein the stirring speed is 200r/min, and the stirring time is 2h, so as to obtain the LED packaging adhesive capable of deep UV curing.
Comparative example 1
Comparative example 1 differs from example 1 only in the preparation method of urethane acrylate, the components of the LED encapsulation cement, the addition amounts of the components, and the preparation method are the same as example 1, and the preparation method of urethane acrylate of comparative example 1 adopts the preparation method in the prior art, and specifically includes the following steps:
(1) Adding 1mol of isophorone diisocyanate and 1mol of hydroxyethyl methacrylate into a reaction kettle, then adding 0.53g of dibutyltin dilaurate, and stirring at the temperature of 70 ℃ at the speed of 100r/min for 2.5h;
(2) Adding 0.5mol PEG100, stirring at 70deg.C for 2.5h at a stirring speed of 100 r/min.
Comparative example 2
Comparative example 2 differs from example 2 only in that comparative example 2 uses an equivalent amount of bisphenol a epoxy acrylate instead of the urethane acrylate of example 2, with the exception of example 2.
Comparative example 3
Comparative example 3 differs from example 2 only in that comparative example 3 uses an equivalent amount of trimethylolpropane triacrylate instead of the tetrahydrofuranacrylate of example 2, otherwise identical to example 2.
Comparative example 4
Comparative example 4 differs from example 2 only in that comparative example 4 uses an equivalent amount of dibenzoyl instead of 2, 2-diethoxy-1-hexanone of example 2, with the exception of example 2.
Comparative example 5
Comparative example 5 differs from example 5 only in that 10 parts of tripropylene glycol diacrylate, 2 parts of 1-hydroxycyclohexyl phenyl ketone, and the other components as in example 5 are added to comparative example 5.
Performance test:
(1) The urethane acrylates prepared in example 1 to 5, comparative example 1 were subjected to viscosity test.
The viscosity test of the polyurethane acrylates was carried out with reference to GB/T2794-2013.
(2) The performance test was performed on the encapsulation adhesives of examples 1-5 and comparative examples 1-5, with the following main test items:
refractive index: tested according to GB/T614-2006.
Transmittance: and placing the packaging adhesive sample into a die with the side length of 50mm multiplied by 50mm and the depth of 1mm, and irradiating for 5s under a UV lamp to obtain a sample wafer with the size of about 50mm multiplied by 1mm, and testing the light transmittance according to GB/T22410-2008.
Depth of cure: and placing the packaging adhesive sample into a die with the side length of 50mm multiplied by 50mm and the depth of 7mm, and irradiating for 10s under a UV lamp to obtain a sample wafer with the size of about 50mm multiplied by 50mm, and testing the thickness of the sample wafer by using a thickness gauge to obtain the curing depth.
(3) The mechanical properties of the encapsulation glues of example 3, example 5, comparative example 3 and comparative example 5 were tested, and the main test items are as follows:
hardness: tested according to GB/T531.1-2008.
Tensile strength: tested according to GB/T528-2009.
The results of the viscosity test of the urethane acrylate prepared in comparative example 1 are shown in Table 1.
The results of the performance test of the encapsulation adhesives of examples 1 to 5 and comparative examples 1 to 5 are shown in Table 2.
The results of the mechanical property tests of example 3, example 5, comparative example 3 and comparative example 5 are shown in Table 3.
TABLE 1
Figure BDA0004105331870000111
As can be seen from Table 1, the viscosity of examples 1-5 is far lower than that of comparative example 1, which shows that the polyurethane acrylate prepared by the preparation method of the invention has a lower viscosity, and the polyurethane acrylate in the viscosity range of 5000-8000 Pa.s can ensure that the packaging adhesive has proper viscosity, so that the packaging adhesive has good curing depth, refractive index, light transmittance and mechanical property, and the sealing and luminous performance requirements of the LED are ensured.
TABLE 2
Test item Viscosity (mPa. S) Refractive index Transmittance (%) Depth of cure (mm)
Example 1 1230 1.5132 95.67 5.34
Example 2 1570 1.5281 95.89 5.26
Example 3 1660 1.5216 96.21 5.42
Example 4 1330 1.5231 96.32 5.28
Example 5 1420 1.5208 95.76 5.19
Comparative example 1 3160 1.5062 90.67 4.98
Comparative example 2 3850 1.4932 88.57 3.26
Comparative example 3 1790 1.4703 87.18 4.76
Comparative example 4 1970 1.4837 91.52 3.28
Comparative example 5 1890 1.4902 90.26 2.35
As shown in Table 2, the viscosity of the encapsulation adhesive of examples 1-5 of the invention is 1200-1700 mPa.s, the viscosity is proper, and the encapsulation adhesive has good refractive index, light transmittance and curing depth, and can well meet the requirements of sealing, protection and luminescence performance of LEDs. The properties of the encapsulation glues of examples 1-5 are significantly better as a whole than those of the encapsulation glues of comparative examples 1-5.
The preparation method of the polyurethane acrylic ester in the comparative example 1 adopts the preparation method in the prior art, and the prepared polyurethane acrylic ester has higher viscosity and has adverse effects on the chromaticity and photopolymerization activity of the product, so that the viscosity of the packaging adhesive is higher, and the refractive index, the light transmittance and the curing depth are lower than those of the example 1. The polyurethane acrylate of example 1 has a low viscosity value, so that the encapsulation cement has a suitable viscosity and good refractive index, light transmittance and curing depth.
Compared with the embodiment 2, the overall performance of the LED packaging adhesive of the comparative examples 2-4 is inferior to that of the embodiment 2, which shows that the polyurethane acrylic ester, the reactive diluent and the photoinitiator are indispensable, and the three components act together, so that the LED packaging adhesive has good viscosity, refractive index, light transmittance and curing depth.
Comparative example 5 reduced reactive diluent addition, reduced photoinitiator addition, such that the polyurethane acrylate, reactive diluent, photoinitiator addition was not at 100: (18-55): (3-12), resulting in overall performance of the LED packaging adhesive being lower than that of example 5, the invention is illustrated by controlling the addition ratio of polyurethane acrylate, reactive diluent and photoinitiator to 100: (18-55): (3-12) can enable the finally prepared LED packaging adhesive to have good viscosity, refractive index, light transmittance and curing depth, and can meet the requirements of sealing, protection and luminous performance of an LED.
TABLE 3 Table 3
Test item Hardness (D) Tensile Strength (MPa)
Example 3 55 9.81
Example 5 56 9.36
Comparative example 3 42 6.82
Comparative example 5 48 8.52
As can be seen from Table 3, the hardness and tensile strength of the sealant of example 3 and example 5 are significantly higher than those of comparative example 3 and comparative example 5, which demonstrates that the sealant prepared by the invention has good mechanical properties. In addition, the addition amounts of the urethane acrylate, the reactive diluent and the photoinitiator in comparative example 5 were not 100: (18-55): in the range of (3-12), the mechanical properties of the LED packaging adhesive are obviously lower than those of the embodiment 5, which shows that the addition ratio of the polyurethane acrylic ester, the reactive diluent and the photoinitiator is controlled to be 100: (18-55): (3-12) can lead the finally prepared LED packaging adhesive to have good mechanical properties.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. The packaging adhesive is characterized by comprising polyurethane acrylic ester, a reactive diluent and a photoinitiator;
the viscosity of the polyurethane acrylic ester at 25 ℃ is 5000-8000 mPa.s;
the content ratio of the polyurethane acrylic ester, the reactive diluent and the photoinitiator is 100: (18-55): (3-12).
2. The packaging adhesive according to claim 1, wherein the packaging adhesive comprises 100 parts by weight of polyurethane acrylate, 18-55 parts by weight of reactive diluent and 3-12 parts by weight of photoinitiator.
3. The encapsulating compound of claim 1, further comprising an antifoaming agent and/or a polymerization inhibitor.
4. The packaging adhesive according to claim 3, wherein the packaging adhesive comprises 100 parts by weight of polyurethane acrylate, 18-55 parts by weight of reactive diluent, 3-12 parts by weight of photoinitiator, 0.3-1.7 parts by weight of defoamer and 0.3-1.7 parts by weight of polymerization inhibitor.
5. The packaging adhesive according to claim 4, wherein the packaging adhesive comprises 100 parts by weight of polyurethane acrylate, 20-50 parts by weight of reactive diluent, 5-10 parts by weight of photoinitiator, 0.5-1.5 parts by weight of defoamer and 0.5-1.5 parts by weight of polymerization inhibitor.
6. The method for preparing the packaging adhesive according to any one of claims 1 to 5, comprising the following steps:
and mixing and stirring the raw material components under the vacuum condition to obtain the LED packaging adhesive.
7. The method according to claim 6, wherein the stirring speed is 90-330r/min and the stirring time is 0.5-3h.
8. The method of preparing the urethane acrylate according to claim 6, comprising the steps of:
(1) Mixing diisocyanate and polyether glycol, adding a catalyst, heating and stirring to obtain a mixture;
(2) And (3) cooling the mixture obtained in the step (1), adding hydroxy methacrylate and p-phenol, and stirring to obtain the polyurethane acrylate.
9. The process of claim 8, wherein in step (1), the molar ratio of the diisocyanate to the polyether glycol is (1.9-2.1): (0.9-1.1); the addition amount of the catalyst accounts for 0.05% -0.2% of the total weight of the diisocyanate and the polyether glycol; the heating temperature of the heating and stirring is 55-105 ℃; the stirring speed of the heating and stirring is 90-330r/min, and the stirring time of the heating and stirring is 1.5-5.5h;
in the step (2), the temperature of the cooling is 40-55 ℃; the stirring speed is 90-330r/min, and the stirring time is 1.5-5.5h;
the molar ratio of the diisocyanate to the hydroxy methacrylate is (0.9-1.1): (0.9-1.1), wherein the added amount of the p-phenol accounts for 0.06-0.14% of the total weight of the diisocyanate, the polyether glycol, the catalyst and the hydroxy methacrylate.
10. Use of the encapsulation glue of any one of claims 1-5 in the field of LED encapsulation.
CN202310190794.1A 2023-03-02 2023-03-02 LED packaging adhesive capable of deep UV curing and preparation method and application thereof Pending CN116333671A (en)

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