Solid polyether alcohol epoxy resin with high humidity and heat resistance as well as preparation method and application of solid polyether alcohol epoxy resin
Solid polyether alcohol epoxy resin prepared by the ring-opening etherification reaction of diols is used as an LED encapsulant, which solves the problem of poor resistance to moisture and heat of epoxy resin and improves its stability and anti-yellowing performance in high temperature and high humidity environments.
Patent Information
- Application Number
- CN202511096992.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-06
- Publication Date
- 2025-11-18
AI Technical Summary
Existing epoxy resins have poor resistance to damp heat in LED encapsulation, which cannot meet the high temperature and high humidity requirements of RGB SMD LEDs, and their resistance to blue light and ultraviolet radiation is insufficient.
Diols were used as raw materials to carry out ring-opening etherification reactions to prepare difunctional solid polyether alcohol epoxy resins. These resins were then mixed with other components to form LED encapsulants, thereby improving their resistance to damp heat.
While ensuring high temperature resistance, the encapsulating adhesive has significantly improved its resistance to damp heat, making it suitable for the high temperature and high humidity environment of LEDs and preventing yellowing and cracking.
Smart Images
Figure CN120965618A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of epoxy resin, in particular to a solid polyether alcohol epoxy resin with high moisture resistance and heat resistance, a preparation method and application thereof. BACKGROUND
[0002] RGB SMD LED is a product composed of three key technologies of "RGB", "SMD" and "LED", RGB represents three basic colors of red (Red), green (Green) and blue (Blue), and millions of colors can be generated through the combination of different brightness, SMD (Surface-Mounted Diode) is a technology of directly mounting light-emitting diode (LED) on the circuit board, which can improve the durability and heat dissipation of LED; therefore, RGB SMD LED combines the advantages of three-color light and SMD packaging technology, and becomes the mainstream choice in modern lighting and display technology.
[0003] RGB SMD LED has very high requirements for the moisture resistance and heat resistance of the packaging glue, and the packaging glue should be able to withstand the high temperature of the LED itself during operation (usually 80-120℃+) and the high temperature of the subsequent reflow soldering process (the peak value of lead-free process is about 260℃); the packaging glue cannot decompose, soften, yellow or crack at this temperature;
[0004] In addition, the packaging glue should have good resistance to the blue light and potential ultraviolet radiation emitted by the LED to prevent its own degradation due to aging, and the light aging resistance of bisphenol A epoxy resin is much weaker than that of alicyclic epoxy resin, so the packaging glue in this part is mostly based on alicyclic epoxy resin;
[0005] In order to improve the high temperature resistance of the packaging glue, it is usually necessary to add solid epoxy resin 3150 (poly[(2-oxiranylmethyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether (3:1)) in the formula, and the solid epoxy resin 3150 is a multifunctional epoxy resin prepared by epoxidation of oligomers, which has similar reactivity with polyether glycidyl ether type epoxy resin due to the terminal epoxy group, and can be effectively cured with various curing agents such as anhydride, phenol, amine and cationic curing agent, and has good electrical insulation, heat resistance and weather resistance; the solid epoxy resin 3150 is a three-functional polyether alcohol epoxy resin, which has poor moisture resistance and heat resistance due to the presence of more ether bonds and exposed hydroxyl groups in its structure.
[0006] In view of the above, it is necessary to improve the existing preparation of epoxy resin to adapt to the needs of the use of new epoxy resin. SUMMARY
[0007] To address the aforementioned technical problems, this invention provides a solid polyether alcohol epoxy resin with high resistance to damp heat, wherein the target compound I of the epoxy resin has the following structural formula:
[0008]
[0009] The average value of n is 5.
[0010] As a further supplement to this technical solution, the structural formula of the epoxy resin target compound II is:
[0011]
[0012] The average value of n is 5.
[0013] As a further supplement to this technical solution, the reaction equation for target compound I is as follows:
[0014]
[0015] As a further supplement to this technical solution, the reaction equation for the target compound II is as follows:
[0016]
[0017] A method for preparing a solid polyether alcohol epoxy resin with high resistance to damp heat includes the following steps:
[0018] Step (1): In a reactor, a diol with a rigid structure is polymerized with 4-vinylepoxycyclohexane to generate a polyether polyol oligomer with double bonds.
[0019] Step (2): The polyether polyol oligomer generated in step one is epoxidized with peracetic acid to obtain a high heat-resistant solid polyether polyol epoxy resin product.
[0020] A high-humidity- and heat-resistant solid polyether alcohol epoxy resin prepared as described above is used in LED lamp bead encapsulation adhesive.
[0021] A method for preparing an LED bead encapsulating adhesive includes the following steps:
[0022] Preparation of component A: 60 parts by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylic acid ester, 20 parts of the above-mentioned target compound I solid epoxy resin, 20 parts of E51 epoxy resin, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of BYK-A530 were weighed according to the specified proportions and stirred at 90°C for 1 hour until a uniform, transparent, homogeneous phase was obtained.
[0023] Preparation of component B: After weighing 100 parts of methyl hexahydrophthalic anhydride, 2 parts of Hycat AO-4 and 3 parts of polybutylene adipate in proportion, stir at room temperature for 1 hour until a uniform transparent homogeneous phase is formed.
[0024] After thoroughly mixing component A and component B at a weight ratio of A:B = 100:104 and removing air bubbles, the mixture is applied to the LED beads, heated at 120°C for 1 hour, then heated at 150°C for 3 hours, and cooled to room temperature to obtain the encapsulated LED beads.
[0025] A method for preparing an LED bead encapsulating adhesive includes the following steps:
[0026] Preparation of component A: 60 parts by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 20 parts of the above-mentioned target compound II solid epoxy resin, 20 parts of E51 epoxy resin, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of BYK-A530 were weighed according to the specified proportions and stirred at 90°C for 1 hour until a uniform, transparent, homogeneous phase was obtained.
[0027] Preparation of component B: After weighing 100 parts of methyl hexahydrophthalic anhydride, 2 parts of Hycat AO-4 and 3 parts of polybutylene adipate in proportion, stir at room temperature for 1 hour until a uniform transparent homogeneous phase is formed.
[0028] After thoroughly mixing component A and component B at a weight ratio of A:B = 100:103 and removing air bubbles, the mixture is applied to the LED beads, heated at 120°C for 1 hour, then heated at 150°C for 3 hours, and cooled to room temperature to obtain the encapsulated LED beads.
[0029] Its beneficial effect is that the present invention uses diol as raw material to carry out ring-opening etherification reaction to prepare a difunctional solid polyether alcohol epoxy resin. Under the premise of ensuring that its high temperature resistance does not change significantly, its damp heat resistance is significantly improved, thereby improving the damp heat resistance of LED encapsulant. Detailed Implementation
[0030] To facilitate a clearer understanding of this technical solution by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to embodiments:
[0031] Example 1
[0032] 19.8 g (0.1 mol) of 4,4'-dihydroxycyclohexane and 124 g (1.0 mol) of 4-vinylepoxycyclohexane were added to a 1 L dry three-necked flask and placed in a water bath. The mixture was heated with stirring. When the temperature inside the flask reached 20–40 °C, a catalyst solution prepared by 3.9 g (0.027 mol) of boron trifluoride diethyl ether complex and 50 g of ethyl acetate was added dropwise. The dropwise addition took about 1.5 hours. After the addition was completed, the reaction was maintained at 40–65 °C and continued for about 1.5 hours. A sample was then taken for GC analysis. When the residual 4-vinylepoxycyclohexane was less than 2.5%, the reaction was considered complete. 340 g of ethyl acetate was added to the flask and the mixture was stirred to lower the temperature. When the internal temperature dropped below 30 °C, 70 g of 10% NaOH aqueous solution was added to the flask, and the mixture was stirred and washed for 30 minutes before phase separation. The upper organic phase is washed with 150g of aqueous solution for 30 minutes, allowed to stand and separate, and the lower polymer organic phase is separated for later use.
[0033] The above polymer organic phase was transferred to a 2L three-necked flask, and a certain amount of sodium acetate trihydrate was added. The flask was then placed in a low-temperature reaction bath to cool down. Once the temperature inside the flask dropped to 20°C, 400g of a pre-prepared peracetic acid solution (26% peracetic acid concentration) was added dropwise over approximately 2 hours. After the addition was complete, the reaction was maintained at 20–46°C for 15 hours. After the reaction was complete, 200g of ethyl acetate was added to the flask, followed by washing with 200g of water for 30 minutes. The lower aqueous phase was separated, and the upper organic phase was washed again with 200mL of deionized water, 200mL of 10% alkali solution, and 200mL of deionized water. The qualified organic phase was subjected to vacuum depressurization to remove ethyl acetate, yielding 140.5g of the target compound I product as a colorless solid, with a molar yield of 87.9%.
[0034] APHA color 7 (25% acetone solution), softening point 70℃, epoxy equivalent 185.
[0035] Example 2
[0036] 24 g (0.1 mol) of hydrogenated bisphenol A and 124 g (1.0 mol) of 4-vinylepoxycyclohexane were added to a 1 L dry three-necked flask. The flask was placed in a water bath and heated with stirring. When the temperature inside the flask reached 20–40 °C, a catalyst solution prepared by 3.9 g (0.027 mol) of boron trifluoride diethyl ether complex and 50 g of ethyl acetate was added dropwise. The dropwise addition took about 1.5 hours. After the dropwise addition was completed, the reaction was maintained at 40–65 °C and continued for about 1.5 hours. A sample was then taken for GC analysis. When the residual 4-vinylepoxycyclohexane was less than 2.5%, the reaction was considered complete. 340 g of ethyl acetate was added to the flask and the temperature was lowered with stirring. When the internal temperature dropped below 30 °C, 70 g of 10% NaOH aqueous solution was added to the flask. After stirring and washing for 30 min, the phases were separated. The upper organic phase was then washed with 150 g of aqueous solution for 30 min, allowed to stand, and the lower polymer organic phase was separated for later use.
[0037] The above polymer organic phase was transferred to a 2L three-necked flask, and a certain amount of sodium acetate trihydrate was added. The flask was then placed in a low-temperature reaction bath to cool down. Once the temperature inside the flask dropped to 20°C, 400g of a pre-prepared peracetic acid solution (26% peracetic acid concentration) was added dropwise over approximately 2 hours. After the addition was complete, the reaction was maintained at 20–46°C for 15 hours. After the reaction was complete, 200g of ethyl acetate was added to the flask, followed by washing with 200g of water for 30 minutes. The lower aqueous phase was separated, and the upper organic phase was washed again with 200mL of deionized water, 200mL of 10% alkali solution, and 200mL of deionized water. The qualified organic phase was subjected to vacuum desulfurization to remove ethyl acetate, yielding 150g of the target compound II product, a colorless and transparent solid with a molar yield of 91.5%.
[0038] APHA color 6 (25% acetone solution), softening point 73℃, epoxy equivalent 196.
[0039] In this invention, 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester is TTA21P produced by our company, CAS No.: 2386-87-0;
[0040] Solid epoxy resin 3150 is our company's own TTA3150, CAS number: 244772-00-7;
[0041] Bisphenol A epoxy resin E51 was purchased from Nan Ya Epoxy Resin (Kunshan) Co., Ltd., CAS No. 25085-99-8, with an epoxy value of 0.48-0.54;
[0042] Methylhexahydrophthalic anhydride was purchased from Aladdin Reagent, CAS No.: 25550-51-0;
[0043] Hycat AO-4 was purchased from DTCS in the United States;
[0044] BYK-A530 was purchased from BYK in Germany;
[0045] Polybutylene adipate was purchased from Aladdin Reagent, CAS No.: 150923-12-9;
[0046] 2,6-Di-tert-butyl-4-methylphenol was purchased from Aladdin Reagent, CAS No.: 128-37-0;
[0047] Application Example 1:
[0048] Preparation of resin compositions and their use in LED chip encapsulation
[0049] Preparation of component A: 60 parts by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylic acid ester, 20 parts of the above-mentioned target compound I solid epoxy resin, 20 parts of E51 epoxy resin, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of BYK-A530 were weighed according to the specified proportions and stirred at 90°C for 1 hour until a uniform, transparent, homogeneous phase was obtained.
[0050] Preparation of component B: After weighing 100 parts of methyl hexahydrophthalic anhydride, 2 parts of Hycat AO-4 and 3 parts of polybutylene adipate in proportion, stir at room temperature for 1 hour until a uniform transparent homogeneous phase is formed.
[0051] After thoroughly mixing component A and component B at a weight ratio of A:B = 100:104 and removing air bubbles, the mixture is applied to the LED beads, heated at 120°C for 1 hour, then heated at 150°C for 3 hours, and cooled to room temperature to obtain the encapsulated LED beads.
[0052] Application Example 2:
[0053] Preparation of resin compositions and their use in LED chip encapsulation
[0054] Preparation of component A: 60 parts by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 20 parts of the above-mentioned target compound II solid epoxy resin, 20 parts of E51 epoxy resin, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of BYK-A530 were weighed according to the specified proportions and stirred at 90°C for 1 hour until a uniform, transparent, homogeneous phase was obtained.
[0055] Preparation of component B: After weighing 100 parts of methyl hexahydrophthalic anhydride, 2 parts of Hycat AO-4 and 3 parts of polybutylene adipate in proportion, stir at room temperature for 1 hour until a uniform transparent homogeneous phase is formed.
[0056] After thoroughly mixing component A and component B at a weight ratio of A:B = 100:103 and removing air bubbles, the mixture is applied to the LED beads, heated at 120°C for 1 hour, then heated at 150°C for 3 hours, and cooled to room temperature to obtain the encapsulated LED beads.
[0057] Comparative Example 1:
[0058] Preparation of resin compositions and their use in LED chip encapsulation
[0059] Preparation of component A: 60 parts by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylic acid ester, 20 parts of TTA3150, 20 parts of E51 epoxy resin, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of BYK-A530 were weighed according to the specified proportions and stirred at 90°C for 1 hour until a uniform, transparent, homogeneous phase was obtained.
[0060] Preparation of component B: After weighing 100 parts of methyl hexahydrophthalic anhydride, 2 parts of Hycat AO-4 and 3 parts of polybutylene adipate in proportion, stir at room temperature for 1 hour until a uniform transparent homogeneous phase is formed.
[0061] After thoroughly mixing component A and component B at a weight ratio of A:B = 100:105 and removing air bubbles, the mixture is applied to the LED beads, heated at 120°C for 1 hour, then heated at 150°C for 3 hours, and cooled to room temperature to obtain the encapsulated LED beads.
[0062] Comparative Example 2:
[0063] Preparation of resin compositions and their use in LED chip encapsulation
[0064] Preparation of component A: 80 parts by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylic acid ester, 20 parts of E51 epoxy resin, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol and 0.2 parts of BYK-A530 were weighed according to the specified ratio and stirred at 90°C for 1 hour until a uniform, transparent, homogeneous phase was formed.
[0065] Preparation of component B: After weighing 100 parts of methyl hexahydrophthalic anhydride, 2 parts of Hycat AO-4 and 3 parts of polybutylene adipate in proportion, stir at room temperature for 1 hour until a uniform transparent homogeneous phase is formed.
[0066] After thoroughly mixing component A and component B at a weight ratio of A:B = 100:112 and removing air bubbles, the mixture is applied to the LED beads, heated at 120°C for 1 hour, then heated at 150°C for 3 hours, and cooled to room temperature to obtain the encapsulated LED beads.
[0067] Test case
[0068] Moisture and heat resistance test:
[0069] The packaged LED chips from Application Case 1-2 and Comparative Example 1-2 were placed in an chamber at 85℃ and 85% humidity for 0h, 24h, 48h, 72h, and 96h, respectively. Then, the LED chips were removed and reflow soldered (from 150℃ to 260℃ for 10min) three times, and the peeling or cracking was observed. The results are shown in Table 1.
[0070] Table 1 Results of Damp Heat Resistance Test
[0071]
[0072] As can be seen from Table 1, the moisture and heat resistance of the encapsulating adhesive after curing is better than that after adding TTA3150, and even better than that without adding any solid epoxy resin 3150.
[0073] The above technical solutions only embody the preferred technical solutions of the present invention. Any modifications that may be made by those skilled in the art to certain parts thereof embody the principles of the present invention and fall within the protection scope of the present invention.
Claims
1. A solid polyether alcohol epoxy resin with high resistance to damp heat, characterized in that, The structural formula of the target epoxy resin compound I is: The average value of n is 5.
2. The high moisture- and heat-resistant solid polyether alcohol epoxy resin according to claim 1, characterized in that, The structural formula of the target epoxy resin compound II is: The average value of n is 5.
3. The high moisture-heat resistant solid polyether alcohol epoxy resin according to claim 1, characterized in that, The reaction equation for target compound I is:
4. The high moisture-heat resistant solid polyether alcohol epoxy resin according to claim 2, characterized in that, The reaction equation for target compound II is:
5. A method for preparing a highly moisture-resistant solid polyether alcohol epoxy resin according to any one of claims 1-4, characterized in that, Includes the following steps: Step (1): In a reactor, a diol with a rigid structure is polymerized with 4-vinylepoxycyclohexane to generate a polyether polyol oligomer with double bonds. Step (2): The polyether polyol oligomer generated in step one is epoxidized with peracetic acid to obtain a high heat-resistant solid polyether polyol epoxy resin product.
6. A highly moisture- and heat-resistant solid polyether alcohol epoxy resin prepared according to any one of claims 1-4 or claim 5 is used in LED lamp bead encapsulation adhesive.
7. The method for preparing an LED bead encapsulating adhesive according to claim 6, characterized in that, Includes the following steps: Preparation of component A: 60 parts by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylic acid ester, 20 parts of the above-mentioned target compound I solid epoxy resin, 20 parts of E51 epoxy resin, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of BYK-A530 were weighed according to the specified proportions and stirred at 90°C for 1 hour until a uniform, transparent, homogeneous phase was obtained. Preparation of component B: After weighing 100 parts of methyl hexahydrophthalic anhydride, 2 parts of Hycat AO-4 and 3 parts of polybutylene adipate in proportion, stir at room temperature for 1 hour until a uniform transparent homogeneous phase is formed. After thoroughly mixing component A and component B at a weight ratio of A:B = 100:104 and removing air bubbles, the mixture is applied to the LED beads, heated at 120°C for 1 hour, then heated at 150°C for 3 hours, and cooled to room temperature to obtain the encapsulated LED beads.
8. The method for preparing an LED bead encapsulating adhesive according to claim 6, characterized in that, Includes the following steps: Preparation of component A: 60 parts by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 20 parts of the above-mentioned target compound II solid epoxy resin, 20 parts of E51 epoxy resin, 0.6 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.2 parts of BYK-A530 were weighed according to the specified proportions and stirred at 90°C for 1 hour until a uniform, transparent, homogeneous phase was obtained. Preparation of component B: After weighing 100 parts of methyl hexahydrophthalic anhydride, 2 parts of Hycat AO-4 and 3 parts of polybutylene adipate in proportion, stir at room temperature for 1 hour until a uniform transparent homogeneous phase is formed. After thoroughly mixing component A and component B at a weight ratio of A:B = 100:103 and removing air bubbles, the mixture is applied to the LED beads, heated at 120°C for 1 hour, then heated at 150°C for 3 hours, and cooled to room temperature to obtain the encapsulated LED beads.