WO2022148103A1 - 一种预聚体、含有该预聚体的封装树脂及封装树脂的应用 - Google Patents

一种预聚体、含有该预聚体的封装树脂及封装树脂的应用 Download PDF

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WO2022148103A1
WO2022148103A1 PCT/CN2021/126349 CN2021126349W WO2022148103A1 WO 2022148103 A1 WO2022148103 A1 WO 2022148103A1 CN 2021126349 W CN2021126349 W CN 2021126349W WO 2022148103 A1 WO2022148103 A1 WO 2022148103A1
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weight
prepolymer
parts
resin
cas
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French (fr)
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谭晓华
单秋菊
于会云
孙绪筠
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天津德高化成光电科技有限责任公司
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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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • H01L33/483—Containers
    • H01L33/486—Containers adapted for surface mounting
    • 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
    • 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
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the present invention relates to the technical field of thermosetting encapsulation molding materials, in particular to a prepolymer, an encapsulation resin containing the prepolymer and the application of the encapsulation resin.
  • LED Light Emitting Diode
  • the packaging of LED lighting and RGB display devices mostly adopts pre-injection cups on resin substrates and metal brackets, and then pours or dispenses liquid packaging materials in the reflection cups. After the packaging materials are thermally cured, they form an integrated LED packaging structure with the reflection cups. .
  • the reflector cup is not only the carrier of the liquid encapsulation material, but also undertakes to reflect the light emission of the LED chip, forming a single-sided light-emitting structure with a direct upward (Top View).
  • the white light illumination device is packaged with a white reflector cup to enhance the light extraction efficiency, and the RGB display device uses a black reflector cup to improve the contrast ratio of the display.
  • the white light LED uses a blue light chip with an emission wavelength of 450-470 nm as the light source, and emits yellow light by exciting the yellow phosphor mixed in the encapsulation resin, and finally the yellow light and the blue light are synthesized into white light.
  • the white light device reflector cup first used PPA (polyphthalamide resin) material.
  • PPA polyphthalamide resin
  • thermoplastic material As a thermoplastic material, it has obvious advantages such as easy injection molding, strong flexibility, and low cost. It is very suitable for low-power white light LED packaging of 0.5-1W.
  • the blue light chip has a strong photodegradation effect on the PPA resin, resulting in yellowing of the material, which in turn leads to a decrease in the reflectivity of the reflector cup material and damage to the light output of the LED chip.
  • white LED chips when applied to lamps, they need to undergo a reflow soldering surface mount process at a high temperature of up to 260°C. Thermoplastic PPA is prone to deformation and thermal expansion stress at high temperatures, which damages the LED lamp beads.
  • thermosetting epoxy reflector material with triazine derivative epoxy resin or alicyclic epoxy resin as the core component appeared in the market, which is called "EMC bracket”.
  • EMC bracket This type of epoxy resin does not contain a benzene ring structure, which greatly improves the blue light resistance of EMC brackets compared to PPA materials. Because it is a thermosetting material, it has excellent resistance to reflow soldering thermal deformation. The industry even adopts this material.
  • the packaged white light chips are called EMC lamp beads.
  • the EMC reflector bracket has obvious advantages in blue light resistance and heat resistance compared with PPA thermoplastic materials, there is still a blue light resistance problem in LED products with strong power (2-3W). Yellowing remains a major focus.
  • a first aspect of the present invention provides a prepolymer, and the preparation raw materials of the prepolymer include:
  • the raw material for preparing the prepolymer also includes (D) an inhibitor.
  • a second aspect of the present invention provides a method for preparing the above-mentioned prepolymer, comprising the steps of: mixing 100 parts by weight of (A) a compound having the structure shown in formula 1 with (B) a compound containing a phenyl group and Si The -H group organosiloxane and (D) inhibitor are melted at 60-150°C, mixed evenly and then cooled to 60-120°C, (C) platinum catalyst is added, and stirred for 5-15 hours to obtain a prepolymer.
  • a third aspect of the present invention provides an encapsulation resin, and the preparation raw materials of the encapsulation resin include epoxy resin, the above-mentioned prepolymer, a curing agent, an adhesion promoter, and a catalyst.
  • a fourth aspect of the present invention provides a method for preparing an encapsulation resin as described above, comprising the following steps: taking epoxy resin and prepolymer, stirring at 100-150° C., adding a curing agent, and promoting adhesion agent, catalyst, stirring, discharging, cooling, pulverizing, and beating to obtain encapsulation resin.
  • a fifth aspect of the present invention provides an encapsulation resin for a white reflective cup, the preparation raw materials of which include 100 parts by weight of the encapsulating resin as described above and 50-400 parts by weight of titanium dioxide.
  • the sixth aspect of the present invention provides an application of the above-mentioned encapsulation resin for a white reflective cup, which is used in a white LED device with a power of 1-3W.
  • a seventh aspect of the present invention provides an encapsulating resin for a black reflector cup, the preparation raw materials of which include 100 parts by weight of the encapsulating resin as described above and 1-30 parts by weight of carbon black.
  • the eighth aspect of the present invention provides an application of the above-mentioned encapsulation resin for a black reflective cup, which is used for a surface-mounted SMT light-emitting device of an outdoor RGB display screen.
  • a ninth aspect of the present invention provides an LED device, in which a reflector cup structure is obtained by injection molding a metal frame or a resin substrate and the encapsulating resin as described above.
  • the present invention provides a prepolymer, which uses a specific compound to combine with organic silicon, which increases the compatibility of organic silicon and epoxy resin.
  • the process is simple and easy to operate, and the yield is high, which is convenient for further production of high-performance encapsulation resin.
  • the encapsulating resin in the present invention generates thermosetting epoxy resin through the reaction of epoxy component and curing agent, has excellent performance of resisting photoaging in the blue light band of 450nm-470nm, has excellent heat resistance, is easy to encapsulate, has good transparency, and has a wide range of properties. market prospects.
  • FIG. 1 is the test result of UV resistance performance of Example 9 and Comparative Example 1 of the present invention.
  • FIG. 2 is the UV resistance test results of Example 16 and Comparative Example 2 of the present invention.
  • a first aspect of the present invention provides a prepolymer, and its preparation raw materials include:
  • At least one of the R 1 , R 2 , and R 3 is a vinyl group; further preferably, at least one of the R 1 , R 2 , and R 3 is a vinyl group, and at least one is an epoxy group.
  • Examples of (A) the compound having the structure shown in Formula 1 specific examples include DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8), MA-DGIC (Monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9).
  • the phenyl group is located on the side chain of the organosiloxane.
  • the Si-H groups are located on the side chains and/or end groups of the organosiloxane.
  • the organosiloxane in the present invention can be commercially available, for example, RH-309 produced by Ningbo Runhe High-tech Materials Technology Co., Ltd., phenyl crosslinking agent series products produced by Ambiya Special Silicone (Nantong) Co., Ltd., etc. .
  • the Si-H group content in the (B) organosiloxane containing phenyl and Si-H groups is the same as that in (A) the compound having the structure shown in formula 1
  • the molar ratio of vinyl content is (0.2-1):1; further preferably, the Si-H group content in the (B) organosiloxane containing phenyl and Si-H groups is the same as (A)
  • the molar ratio of the vinyl content in the compound having the structure shown in Formula 1 is (0.25-0.95):1.
  • the inventor introduced a siloxane structure into the material. Since the Si-O-Si siloxane structure bond energy of silicone is higher than the C-C bond energy of epoxy resin Larger, it can effectively improve the yellowing and improve the heat resistance of the material. However, the properties of organosiloxane and epoxy resin are quite different, resulting in poor compatibility between the two. In further exploration, the inventor found that using a specific epoxy compound and organosiloxane to make a prepolymer, and then introducing the prepolymer into the encapsulating resin, can greatly improve the performance of the organosiloxane in the epoxy resin system.
  • phenyl-containing silicone is beneficial to reduce the processing viscosity of the encapsulation resin and make the encapsulation operation easier.
  • the phenyl group is easily oxidized to form a quinone, and the material turns yellow.
  • the steric hindrance effect can reduce the interaction force between molecular chains and increase the migration performance of molecular chains. Therefore, in order to balance the operability and UV resistance of the material, the proportion of raw materials of the prepolymer needs to be controlled within a certain range.
  • the platinum catalyst in the present invention is used to catalyze the addition reaction between the silicon-hydrogen bond and the double bond, and can be commercially available, such as a caster platinum catalyst.
  • the amount of the (C) platinum catalyst used is 0.05-1 wt % of (A) the compound having the structure shown in formula 1; further preferably, the amount of the (C) platinum catalyst used is (A) 0.1 to 0.5 wt % of the compound having the structure shown in Formula 1.
  • the raw materials for preparing the prepolymer further include (D) an inhibitor.
  • the inhibitor in the present invention is used to reduce the chemical reaction rate, and its type is not particularly limited, and can be any one well-known to those skilled in the art, such as maleate inhibitor, fumarate inhibitor, organic phosphine inhibitor agents, acetylene inhibitors, etc.
  • the inhibitor is selected from 3,7,11-trimethyldodecyn-3-ol (CAS number: 1604-35-9, TMDO for short), 3,5-dimethyl Alkyl-1-hexyn-3-ol, 3,6-dimethyl-1-heptyn-3-ol, diethyl fumarate, acetylene cyclohexanol (CAS number: 78-27-3), A mixture of one or more of methyl butynol (CAS number: 115-19-5) and methyl maleate.
  • the amount of the (D) inhibitor used is 0 to 0.1 wt % of (A) the compound having the structure shown in formula 1, except for 0; further preferably, the (D) inhibitor
  • the dosage of the agent is 0.01-0.05 wt% of (A) the compound having the structure shown in formula 1.
  • the second aspect of the present invention provides a method for preparing the above-mentioned prepolymer, comprising the following steps: mixing 100 parts by weight of (A) a compound having the structure shown in formula 1 with (B) a compound containing phenyl and Si-H groups Organosiloxane and (D) inhibitor are melted at 60-150°C, mixed evenly and then cooled to 60-120°C, (C) platinum catalyst is added, and stirred for 5-15 hours to obtain a prepolymer.
  • a third aspect of the present invention provides an encapsulation resin, the preparation raw materials of which include: epoxy resin, the above-mentioned prepolymer, a curing agent, an adhesion promoter, and a catalyst.
  • the epoxy resin is selected from triglycidyl isocyanurate (TGIC, CAS No.: 2451-62 -9) Mixing of one or more of cycloaliphatic epoxy resin (CAS number: 3130-19-6) and hydrogenated bisphenol A epoxy resin; further preferably, the epoxy resin is a tricyclic epoxy resin Oxypropyl isocyanurate and/or cycloaliphatic epoxy resin.
  • the weight ratio of the epoxy resin to the prepolymer is (3-20):1; further preferably, the ring The weight ratio of oxygen resin to prepolymer is (4-10):1.
  • the curing agent is an acid anhydride curing agent; further preferably, the acid anhydride curing agent is selected from the group consisting of phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, hydrogenated pyromellitic anhydride Formic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tauric anhydride, dodecenylbutyl dianhydride, nadic anhydride, methyl nadic anhydride, glutaric anhydride, hydrogenated methyl nadic anhydride, methylcyclohexene tetracarboxylic dianhydride, polyazelaic anhydride, polysebacic anhydride, 1,4,5 , a mixture of one or more of 6-tetrabromophthal
  • the amount of the acid anhydride curing agent is calculated according to the molar ratio of the acid anhydride group content to the epoxy group content of the system as (0.8-1):1.
  • the epoxy group content of the system described herein is the sum of the epoxy group content in the epoxy resin and the prepolymer.
  • the adhesion promoter is selected from the group consisting of ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxypropylmethyldimethoxysilane, ⁇ -Methacryloxypropylmethyldiethoxysilane, ⁇ -(2,3-glycidoxy)propyltriethoxysilane, ⁇ -(2,3-glycidoxy) Propylmethyldimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2,4,6,8-Tetra[2-(3,4-epoxycyclohexylethyl)tetramethylcyclotetrasiloxane, 2,4,6-tris[2-(3,4-epoxy cyclohexylethyl)]
  • the dosage of the adhesion promoter is 0.01-5wt% of the total amount of epoxy resin and prepolymer; further preferably, the dosage of the adhesion promoter is epoxy resin 0.05 ⁇ 3wt% of the total amount of prepolymer.
  • the catalyst is selected from triphenylphosphine, methyl trioctyl phosphonium dimethyl phosphate, tetrabutyl phosphonium acetate, methyl tributyl phosphonium dimethyl phosphate, Benzyltriphenylphosphonium chloride, tetrabutylphosphonium chloride, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, benzimidazole a mixture of one or more.
  • the dosage of the catalyst is 0.01-5 wt% of the total amount of epoxy resin, prepolymer and curing agent; further preferably, the dosage of the catalyst is epoxy resin, prepolymer, 0.1-1 wt% of the total amount of curing agent.
  • the preparation raw materials of the encapsulating resin further include at least one of pigments, inorganic fillers, antioxidants, and anti-ultraviolet absorbers.
  • the addition amount can be 1-400 wt% of the total amount of epoxy resin, prepolymer, and curing agent; as inorganic fillers, silica, alumina, calcium carbonate, kaolin can be used as examples etc., the addition amount can be 50-800wt% of the total amount of epoxy resin, prepolymer and curing agent; as antioxidant, 2,6-di-tert-butyl-4-methylphenol, antioxidant 1010 , antioxidant 1076, etc., the addition amount can be 0.01-5wt% of the total amount of epoxy resin, prepolymer and curing agent; as anti-ultraviolet absorber, UV-326, UV-531, UV-234, UV -320, etc., the addition amount can be 0.01-5 wt% of the total amount of epoxy resin, prepolymer and curing agent.
  • a fourth aspect of the present invention provides a method for preparing the above-mentioned encapsulation resin, comprising the following steps: taking epoxy resin and the above-mentioned prepolymer, stirring at 150-200° C., then cooling to 100-150° C., adding and curing agent, adhesion promoter, catalyst, stirring, discharging, cooling, pulverizing and beating to obtain encapsulation resin.
  • a fifth aspect of the present invention provides an encapsulation resin for a white reflector cup, the preparation raw materials of which include 100 parts by weight of the encapsulation resin and 50-400 parts by weight of titanium dioxide.
  • the sixth aspect of the present invention provides an application of the above-mentioned encapsulating resin for a white reflective cup, which is used in a white LED device with a power of 1-3W.
  • a seventh aspect of the present invention provides an encapsulation resin for a black reflector cup, the preparation raw materials of which include 100 parts by weight of the encapsulation resin and 1-30 parts by weight of carbon black.
  • the eighth aspect of the present invention provides an application of the above-mentioned encapsulation resin for a black reflective cup, which is used for a surface-mounted SMT light-emitting device of an outdoor RGB display screen.
  • a ninth aspect of the present invention provides an LED device, in which a reflector cup structure is obtained by injection molding a metal frame or a resin substrate and the above-mentioned encapsulating resin.
  • the reflective cup is not only a carrier when the LED is encapsulated with liquid potting glue, but also a reflective material constituting the single-sided light emission of the LED.
  • the reflective cup is made of the above-mentioned encapsulating resin, which can improve the heat resistance of the LED device. and light aging resistance.
  • Example 1 provides a prepolymer, 100 parts by weight of DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and RH-SH309 (phenyl containing Hydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-tech Materials Technology Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodecyn-3-ol (CAS No.: 1604-35 -9, TMDO for short) was melted at 100°C for 0.5h, mixed uniformly and then cooled to 90°C, added 0.5 parts by weight of PT5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.), stirred for 10h to obtain a aggregates.
  • DA-MGIC diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8
  • RH-SH309 phenyl
  • the amount of RH-SH309 calculated according to the molar ratio of SiH content in RH-SH309 to vinyl content in DA-MGIC is 0.95:1.
  • Example 2 provides a prepolymer, 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9) and RH-SH309 (phenyl containing Hydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-tech Materials Technology Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodecyn-3-ol (CAS No.: 1604-35 -9, TMDO for short) was melted at 100°C for 0.5h, mixed uniformly and then cooled to 90°C, added 0.5 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.), stirred for 10h to obtain prepolymer.
  • MA-DGIC monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9
  • RH-SH309 phenyl
  • the amount of RH-SH309 calculated according to the molar ratio of SiH content in RH-SH309 to vinyl content in MA-DGIC is 0.95:1.
  • Example 3 provides a prepolymer, 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9) and RH-SH309 (phenyl containing Hydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-tech Materials Technology Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodecyn-3-ol (CAS No.: 1604-35 -9, TMDO for short) was melted at 90°C for 0.5h, mixed uniformly and then cooled to 80°C, added 0.5 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.), and stirred for 8h to obtain prepolymer.
  • MA-DGIC monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9
  • RH-SH309 phenyl
  • the amount of RH-SH309 calculated according to the molar ratio of SiH content in RH-SH309 to vinyl content in MA-DGIC is 0.5:1.
  • Example 4 provides a prepolymer, 100 parts by weight of DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and RH-SH309 (phenyl containing Hydrogen organosiloxane, hydrogen content 0.87%, purchased from Ningbo Runhe High-tech Materials Technology Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodecyn-3-ol (CAS No.: 1604-35 -9, TMDO for short) was melted at 90°C for 0.5h, mixed uniformly and then cooled to 80°C, added 0.5 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.), and stirred for 8h to obtain prepolymer.
  • DA-MGIC diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8
  • RH-SH309 pheny
  • the amount of RH-SH309 calculated according to the molar ratio of SiH content in RH-SH309 to vinyl content in DA-MGIC is 0.25:1.
  • Example 5 provides a prepolymer, 100 parts by weight of DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and XL-2460 (phenyl containing Hydrogen organosiloxane, SiH content: 3.85mmol/g, purchased from Ambiya Special Silicone (Nantong) Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodecyn-3-ol (CAS No.: 1604-35-9, abbreviated as TMDO) was melted at 90 °C for 0.5 h, mixed evenly and then cooled to 80 °C and added with 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) , and stirred for 6h to obtain a prepolymer.
  • DA-MGIC diallyl monoglycidyl isocyanurate, CAS number: 20395-16
  • the amount of XL-2460 calculated according to the molar ratio of SiH content in XL-2460 to vinyl content in DA-MGIC is 0.5:1.
  • Example 6 provides a prepolymer, 100 parts by weight of DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and XL-2460 (phenyl containing Hydrogen organosiloxane, SiH content: 3.85mmol/g, purchased from Ambiya Special Silicone (Nantong) Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodecyn-3-ol (CAS No.: 1604-35-9, abbreviated as TMDO) was melted at 90 °C for 0.5 h, mixed evenly and then cooled to 80 °C and added with 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) , and stirred for 6h to obtain a prepolymer.
  • DA-MGIC diallyl monoglycidyl isocyanurate, CAS number: 20395-16
  • the amount of XL-2460 calculated according to the molar ratio of SiH content in XL-2460 to vinyl content in DA-MGIC is 0.95:1.
  • Example 7 provides a prepolymer, 100 parts by weight of DA-MGIC (diallyl monoglycidyl isocyanurate, CAS number: 20395-16-8) and XL-2460 (phenyl containing Hydrogen organosiloxane, SiH content: 3.85mmol/g, purchased from Ambiya Special Silicone (Nantong) Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodecyn-3-ol (CAS No.: 1604-35-9, abbreviated as TMDO) was melted at 90 °C for 0.5 h, mixed evenly and then cooled to 80 °C and added with 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.) , and stirred for 6h to obtain a prepolymer.
  • DA-MGIC diallyl monoglycidyl isocyanurate, CAS number: 20395-16
  • the amount of XL-2460 calculated according to the molar ratio of SiH content in XL-2460 to vinyl content in DA-MGIC is 0.25:1.
  • Example 8 provides a prepolymer, 100 parts by weight of MA-DGIC (monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9) and XL-2460 (organosilicon Alkane, SiH content: 3.85mmol/g, purchased from Ambiya Special Silicone (Nantong) Co., Ltd.), 0.05 parts by weight of 3,7,11-trimethyldodecyn-3-ol (CAS No.: 1604- 35-9, referred to as TMDO) was melted at 90°C for 0.5h, mixed uniformly and then cooled to 80°C, added 0.1 parts by weight of PT 5000 (platinum catalyst, concentration 5000ppm, purchased from Shenzhen Kejunchi Technology Co., Ltd.), stirred for 6h, Prepolymers are obtained.
  • MA-DGIC monoallyl diglycidyl isocyanurate, CAS number: 69731-45-9
  • XL-2460 organosilicon Alkane
  • the amount of XL-2460 calculated according to the molar ratio of SiH content in XL-2460 to vinyl content in MA-DGIC is 0.5:1.
  • the reaction involving RH309 is easier to carry out.
  • the degree of difficulty in carrying out the above reaction is judged according to the length of the reaction time and the level of the reaction temperature. If the reaction time is long and the reaction temperature is high, the operability is not good. , poor, the operability and yield (using the titration method to test the epoxy equivalent) of Examples 1-8 are shown in Table 1.
  • Example operability yield Example 1 Difference 55%
  • Example 2 Difference 50% Example 3 good 65%
  • Example 6 Excellent 90%
  • Example 7 Excellent 95%
  • Example 8 Excellent 85%
  • Embodiment 9 provides a kind of encapsulating resin, taking 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 part by weight of 2,6-di-tert-butyl-4 -Cresol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 2, stirred at 180°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic acid Anhydride (CAS No.: 85-42-7), 0.05 parts by weight of 3-mercaptopropyltrimethoxysilane (CAS No.: 4420-74-0), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, pulverizing, and beating to obtain encapsulation resin.
  • TGIC triglycidyl isocyanurate
  • Embodiment 10 provides a kind of encapsulating resin, taking 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Cresol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 4, stirred at 180°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic acid Anhydride (CAS No.: 85-42-7), 0.25 parts by weight of ⁇ -methacryloyloxypropylmethyldimethoxysilane (CAS No.: 14513-34-9), 0.25 parts by weight of ⁇ -(2 , 3-glycidoxy)propylmethyldimethoxysilane (CAS number: 65799-47-5), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2 ), stirring, dischar
  • Embodiment 11 provides a kind of encapsulating resin, taking 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Cresol (CAS number: 2409-55-4), 10 parts by weight of the prepolymer in Example 6, stirred at 150° C.
  • TGIC triglycidyl isocyanurate
  • 2,6-di-tert-butyl-4 -Cresol CAS number: 2409-55-4
  • Embodiment 12 provides a kind of encapsulating resin, taking 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Cresol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 7, stirred at 180°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic acid Anhydride (CAS No.: 85-42-7), 1 part by weight ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane (CAS No.: 3388-04-3), 1 part by weight 2,4 , 6,8-tetra[2-(3,4-epoxycyclohexylethyl)]tetramethylcyclotetrasiloxane (CAS number: 121225-98-7), 1 part by weight of 3-mercaptopropyl
  • Embodiment 13 provides a kind of encapsulating resin, taking 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 part by weight of 2,6-di-tert-butyl-4 -Cresol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 8, stirred at 180°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic acid Anhydride (CAS No.: 85-42-7), 0.05 parts by weight of ⁇ -methacryloyloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.05 parts by weight of 2,4,6,8 -Tetra[2-(3,4-epoxycyclohexylethyl)]tetramethylcyclotetrasiloxane (CAS number: 121225-98-7), 0.5 parts by weight of 2-ethyl-4-methylimidazo
  • Embodiment 14 provides a kind of encapsulating resin, taking 85 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 part by weight of 2,6-di-tert-butyl-4 -Cresol (CAS number: 2409-55-4), 15 parts by weight of the prepolymer in Example 7, stirred at 180°C for 0.5h, cooled to 130°C, and added 130 parts by weight of hexahydrophthalic acid Anhydride (CAS No.: 85-42-7), 0.025 parts by weight ⁇ -methacryloyloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.05 parts by weight 2,4,6,8 -Tetramethyl-2,4,6,8-tetra[3-(oxiranylmethoxy)propyl]cyclotetrasiloxane (CAS No.: 60665-85-2), 0.5 parts by weight 2 -Ethyl-4-methylimid
  • Embodiment 15 provides a kind of encapsulating resin, taking 80 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 parts by weight of 2,6-di-tert-butyl-4 -Cresol (CAS No.: 2409-55-4), 20 parts by weight of the prepolymer in Example 7, stirred at 180°C for 0.5h, cooled to 130°C, added 110 parts by weight of hexahydrophthalic acid Anhydride (CAS No.: 85-42-7), 0.05 parts by weight of ⁇ -methacryloyloxypropyltrimethoxysilane (CAS No.: 2530-85-0), 0.05 parts by weight of 2,4,6,8 -Tetramethyl-2-[3-(oxiranylmethoxy)propyl]cyclotetrasiloxane (CAS No.: 61614-55-9), 0.5 parts by weight of 2-ethyl-4-methyl imidazole (CAS No
  • Embodiment 16 provides a kind of encapsulating resin, taking 90 parts by weight of alicyclic epoxy resin A (bis(7-oxabicyclo[4.1.0]3-heptylmethyl)oxalate), 0.05 parts by weight of 2 , 6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), and 10 parts by weight of the prepolymer in Example 2 were stirred at 180° C.
  • alicyclic epoxy resin A bis(7-oxabicyclo[4.1.0]3-heptylmethyl)oxalate
  • 0.05 parts by weight of 2 6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4)
  • 10 parts by weight of the prepolymer in Example 2 were stirred at 180° C.
  • Embodiment 17 provides an encapsulating resin, comprising 90 parts by weight of cycloaliphatic epoxy resin A, 0.05 part by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), 10 parts by weight of the prepolymer in Example 4 were stirred at 180° C. for 0.5 h, cooled to 130° C., and 110 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.025 part by weight were added.
  • ⁇ -Methacryloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.025 parts by weight of ⁇ -methacryloyloxypropylmethyldiethoxysilane (CAS number: 65100 -04-1), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2), stirring, discharging, cooling, pulverizing, and beating to obtain a packaging resin.
  • Embodiment 18 provides an encapsulating resin, comprising 90 parts by weight of alicyclic epoxy resin A, 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 7 were stirred at 180° C. for 0.5 h, cooled to 130° C., and 110 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.025 part by weight were added.
  • ⁇ -Methacryloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.025 parts by weight of ⁇ -methacryloyloxypropylmethyldiethoxysilane (CAS number: 65100 -04-1), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2), stirring, discharging, cooling, pulverizing, and beating to obtain a packaging resin.
  • Embodiment 19 provides an encapsulating resin, comprising 90 parts by weight of alicyclic epoxy resin A, 0.05 part by weight of 2,6-di-tert-butyl-4-methylphenol (CAS No.: 2409-55-4), 10 parts by weight of the prepolymer in Example 8 were stirred at 180°C for 0.5h, cooled to 130°C, and 110 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.025 part by weight were added.
  • ⁇ -Methacryloxypropyltrimethoxysilane (CAS number: 2530-85-0), 0.025 parts by weight of ⁇ -methacryloyloxypropylmethyldiethoxysilane (CAS number: 65100 -04-1), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS number: 931-36-2), stirring, discharging, cooling, pulverizing, and beating to obtain a packaging resin.
  • Comparative example 1 provides a kind of encapsulating resin, taking 90 parts by weight of triglycidyl isocyanurate (TGIC, CAS number: 2451-62-9), 0.05 part by weight of 2,6-di-tert-butyl-4 -Cresol (CAS No.: 2409-55-4), stirred at 180°C for 0.5h, cooled to 130°C, added 150 parts by weight of hexahydrophthalic dianhydride (CAS No.: 85-42-7), 0.05 parts by weight of 3-mercaptopropyltrimethoxysilane (CAS No.: 4420-74-0), 0.5 parts by weight of 2-ethyl-4-methylimidazole (CAS No.: 931-36-2), stirred, and discharged material, cooled, pulverized, and beaten to obtain encapsulation resin.
  • TGIC triglycidyl isocyanurate
  • CAS No.: 2409-55-4 2,6-di-tert-butyl
  • Comparative example 2 provides a kind of encapsulating resin, taking 90 parts by weight of alicyclic epoxy resin A, 0.05 parts by weight of 2,6-di-tert-butyl-4-methylphenol (CAS number: 2409-55-4), Stir at 180°C for 0.5h, cool down to 130°C, add 110 parts by weight of hexahydrophthalic dianhydride (CAS number: 85-42-7), 0.025 part by weight of ⁇ -methacryloyloxypropyltrimethoxy Silane (CAS No.: 2530-85-0), 0.025 parts by weight of ⁇ -methacryloyloxypropylmethyldiethoxysilane (CAS No.: 65100-04-1), 0.5 parts by weight of 2-ethyl base-4-methylimidazole (CAS No.: 931-36-2), stirring, discharging, cooling, pulverizing, and beating to obtain encapsulation resin.
  • 2-ethyl base-4-methylimidazole CAS No.: 931-36-2
  • Examples 9 to 19 and Comparative Examples 1 to 2 The operability of Examples 9 to 19 and Comparative Examples 1 to 2 was evaluated, and the chips were encapsulated with the encapsulating resin in each example. If the encapsulating resin could not encapsulate the chip, or the melt viscosity was too large, the operability would fail. Not good, the evaluation results of operability are divided into excellent, good, and poor in order from good to poor.
  • Examples 9 to 19 and Comparative Examples 1 to 2 The transparency of Examples 9 to 19 and Comparative Examples 1 to 2 was evaluated.
  • the encapsulation resin was preheated, extruded into the mold cavity, molded and cured at 160°C for 300s, and then cured at 150 to 170°C for 2 to 4 hours to obtain the thickness.
  • Uniform (200 ⁇ 10um) test sample observe whether the molded sample is transparent or milky white.
  • the evaluation results of transparency are divided into excellent, good and poor in the order of transparency, translucency and milky white. Examples 9 to 19, right
  • the transparency of ratios 1 to 2 is shown in Table 2.
  • Example operability transparency UV resistance After UV test b Example 9 Excellent Difference Excellent 5-6
  • Example 10 Excellent Excellent better 6-7
  • Example 11 Excellent Excellent better 6-7
  • Example 12 better better better 6-7
  • Example 13 better better better 6-7
  • Example 14 Excellent better better 6-7
  • Example 15 Excellent better better 6-7
  • Example 16 Excellent Excellent Excellent Excellent 5-6
  • Example 17 Excellent Excellent better 7-9
  • Example 18 Excellent Excellent better 7-9
  • Example 19 Excellent Excellent better 7-9 Comparative Example 1 Excellent better good 6-7 Comparative Example 2 Excellent Excellent good 7-8
  • Example 9 and Comparative Example 1, Example 16 and Comparative Example 2 were found through the UV lamp resistance to blue light light decay test, and the encapsulation resin obtained after adding the prepolymer of the present invention had better resistance to UV light decay, This effect can be seen from FIGS. 1 and 2 .
  • the inventor found that according to a large number of experimental results, in the triglycidyl isocyanurate system, an example is arbitrarily selected from Examples 1 to 8, and according to the conditions of Example 9, an excellent performance can be obtained.
  • the encapsulating resin is used to encapsulate the LED chip, and the LED white light chip with blue light resistance can be obtained.

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Abstract

本发明公开了一种预聚体，所述预聚体的制备原料包括：（A）具有如式（1）所示结构的化合物，式（1）中R1、R2、R3分别独立地选自乙烯基或环氧基；（B）含有苯基和Si-H基团的有机硅氧烷；（C）铂金催化剂。该预聚体采用特定化合物与有机硅结合，增加了有机硅与环氧树脂的相容性，工艺简便易操作，且收率高，便于进一步生产高性能的封装树脂。本发明还提供了一种封装树脂，包括环氧树脂、如上所述的预聚体、固化剂、粘接力促进剂、催化剂。该封装树脂通过环氧组分和固化剂反应生成热固性环氧树脂，具有耐受450nm-470nm蓝光波段光老化的优异性能，同时耐热性能优良，易于封装，透明性好，具有广阔的市场前景。

Description

一种预聚体、含有该预聚体的封装树脂及封装树脂的应用 技术领域
本发明涉及热固性封装成型材料技术领域，尤其涉及一种预聚体、含有该预聚体的封装树脂及封装树脂的应用。
背景技术
LED(Light Emitting Diode)作为发光半导体，已经成为照明、主动RGB显示、LCD背光、车载照明等领域的不可替代光电元器件。LED照明和RGB显示器件的封装多采用在树脂基板和金属支架上预注塑反射杯，然后在反射杯内浇注或点胶填充液态封装材料，封装材料热固化后与反射杯形成一体的LED封装结构。反射杯既是液体封装材料的载体，同时承担反射LED芯片的发光，形成向上直射的(Top View)单面出光结构。白光照明器件采用白色反射杯封装用以增强出光效率，RGB显示器件采用黑色反射杯以提高显示器的对比度。
白光LED采用发射波长450-470nm的蓝光芯片作为光源，通过激发封装树脂中混合的黄色荧光粉发出黄光，最终黄光和蓝光合成为白光。白光器件反射杯最早使用PPA(聚邻苯二甲酸酰胺树脂)材料，作为热塑性材料其易注塑成型、挠性强、成本低等优势明显，非常适合0.5-1W的低功率白光LED封装。而高于1W的LED白光灯珠，蓝光芯片对PPA树脂有强烈的光降解作用而导致材料发生黄变，进而导致反射杯材料的反射率下降、LED芯片出光受损。此外白光LED芯片在应用到灯具时，需经历最高260℃高温的回流焊表面贴装过程，热塑性PPA在高温下易产生形变和热膨胀应力而损坏LED灯珠。
后来市场出现以三嗪衍生物环氧树脂或脂环族环氧树脂为核心成分的热固性环氧树脂反射杯材料，被称为“EMC支架”。此类环氧树脂不含苯环结构，使EMC支架耐蓝光能力较之PPA材料有大幅提升，且因其是热固性材料，耐受回流焊热形变能力也非常优秀，行业甚至把采用这种材料封装的白光芯片称为EMC灯珠。虽然EMC反射杯支架相较PPA热塑性材料耐蓝光、耐热优势明显，但在功率较强(2-3W)的LED产品中仍存在蓝光耐受问题，环氧树脂在长期高温及蓝光照射下，黄变依然是主要的焦点问题。
发明内容
为了解决上述问题，本发明的第一方面提供了一种预聚体，所述预聚体的制 备原料包括：
(A)具有如式1所示结构的化合物，式1：
Figure PCTCN2021126349-appb-000001
其中R 1、R 2、R 3分别独立地选自乙烯基或环氧基；
(B)含有苯基和Si-H基团的有机硅氧烷；
(C)铂金催化剂。
作为一种优选的技术方案，所述预聚体的制备原料还包括(D)抑制剂。
本发明的第二方面提供了一种如上所述的预聚体的制备方法，包括以下步骤：将100重量份(A)具有如式1所示结构的化合物与(B)含有苯基和Si-H基团的有机硅氧烷、(D)抑制剂在60～150℃下融化，混合均匀后降温至60～120℃，加入(C)铂金催化剂，搅拌5～15h，得到预聚体。
本发明的第三方面提供了一种封装树脂，所述封装树脂的制备原料包括环氧树脂、如上所述的预聚体、固化剂、粘接力促进剂、催化剂。
本发明的第四方面提供了一种如上所述的封装树脂的制备方法，包括以下步骤：取环氧树脂、预聚物，在100～150℃下搅拌，，加入固化剂、粘接力促进剂、催化剂，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
本发明的第五方面提供了一种白色反射杯用封装树脂，其制备原料包括100重量份如上所述的封装树脂、50～400重量份二氧化钛。
本发明的第六方面提供了一种如上所述的白色反射杯用封装树脂的应用，其用于功率为1～3W的白光LED器件。
本发明的第七方面提供了一种黑色反射杯用封装树脂，其制备原料包括100重量份如上所述的封装树脂、1～30重量份炭黑。
本发明的第八方面提供了一种如上所述的黑色反射杯用封装树脂的应用，其用于户外RGB显示屏的表贴SMT发光器件。
本发明的第九方面提供了一种LED器件，其由金属框架或树脂基板与如上所述的封装树脂通过注塑得到反射杯结构。
有益效果：本发明提供了一种预聚体，采用特定化合物与有机硅结合，增加了有机硅与环氧树脂的相容性，工艺简便易操作，且收率高，便于进一步生产高性能的封装树脂。本发明中的封装树脂通过环氧组分和固化剂反应生成热固性环氧树脂，具有耐受450nm-470nm蓝光波段光老化的优异性能，同时耐热性能优良，易于封装，透明性好，具有广阔的市场前景。
附图说明
为了进一步解释说明本发明中提供的一种预聚体、含有该预聚体的封装树脂及封装树脂的应用的有益效果，提供了相应的附图，需要指出的是本发明中提供的附图只是所有附图中选出来的个别示例，目的也不是作为对权利要求的限定，所有通过本申请中提供的附图获得的其他相应图谱均应该认为在本申请保护的范围之内。
图1为本发明实施例9与对比例1的耐UV性能测试结果。
图2为本发明实施例16与对比例2的耐UV性能测试结果。
具体实施方式
参选以下本发明的优选实施方法的详述以及包括的实施例可更容易地理解本发明的内容。除非另有限定，本文使用的所有技术以及科学术语具有与本发明所属领域普通技术人员通常理解的相同的含义。当存在矛盾时，以本说明书中的定义为准。
本文中的参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
单数形式包括复数讨论对象，除非上下文中另外清楚地指明。“任选的”或者“任意一种”是指其后描述的事项或事件可以发生或不发生，而且该描述包括事件发生的情形和事件不发生的情形。
说明书和权利要求书中的近似用语用来修饰数量，表示本发明并不限定于该具体数量，还包括与该数量接近的可接受的而不会导致相关基本功能的改变的修正的部分。相应的，用“大约”、“约”等修饰一个数值，意为本发明不限于该精 确数值。在某些例子中，近似用语可能对应于测量数值的仪器的精度。在本申请说明书和权利要求书中，范围限定可以组合和/或互换，如果没有另外说明这些范围包括其间所含有的所有子范围。
此外，本发明要素或组分前的不定冠词“一种”和“一个”对要素或组分的数量要求(即出现次数)无限制性。因此“一个”或“一种”应被解读为包括一个或至少一个，并且单数形式的要素或组分也包括复数形式，除非所述数量明显旨指单数形式。
以下通过具体实施方式说明本发明，但不局限于以下给出的具体实施方式。
为了解决上述问题，本发明的第一方面提供了一种预聚物，其制备原料包括：
(A)具有如式1所示结构的化合物，式1：
Figure PCTCN2021126349-appb-000002
其中R 1、R 2、R 3分别独立地选自乙烯基或环氧基；
(B)含有苯基和Si-H基团的有机硅氧烷；
(C)铂金催化剂。
在一些优选的实施方式中，所述R 1、R 2、R 3中的至少一个为乙烯基；进一步优选的，所述R 1、R 2、R 3中的至少一个为乙烯基，至少一个为环氧基。
作为(A)具有如式1所示结构的化合物的实例，具体可举例DA-MGIC(二烯丙基单缩水甘油基异氰脲酸酯，CAS号：20395-16-8)、MA-DGIC(单烯丙基二缩水甘油基异氰脲酸酯，CAS号：69731-45-9)。
在一些优选的实施方式中，所述(B)含有苯基和Si-H基团的有机硅氧烷中苯基位于有机硅氧烷的侧链。
在一些优选的实施方式中，所述(B)含有苯基和Si-H基团的有机硅氧烷中Si-H基团位于有机硅氧烷的侧链和/或端基。
本发明中的有机硅氧烷可为市售，例如宁波润禾高新材料科技股份有限公司生产的RH-309、安必亚特种有机硅(南通)有限公司生产的苯基交联剂系列产品等。
在一些优选的实施方式中，所述(B)含有苯基和Si-H基团的有机硅氧烷中 的Si-H基团含量与(A)具有如式1所示结构的化合物中的乙烯基含量的摩尔比为(0.2～1)∶1；进一步优选的，所述(B)含有苯基和Si-H基团的有机硅氧烷中的Si-H基团含量与(A)具有如式1所示结构的化合物中的乙烯基含量的摩尔比为(0.25～0.95)∶1。
为了改善封装环氧树脂在LED产品中易黄变的问题，发明人在材料中引入硅氧烷结构，由于有机硅的Si-O-Si硅氧烷结构键能比环氧树脂的C-C键能更大，能够有效改善黄变，同时提高材料的耐热性，然而有机硅氧烷与环氧树脂的性质差异较大，导致两者之间的相容性较差。发明人在进一步的探索中发现，使用特定的环氧化合物与有机硅氧烷制成预聚体，再将预聚体引入封装树脂，可以极大地提高有机硅氧烷在环氧树脂体系中的相容性，进而使封装树脂的操作性能和耐UV性能得到改善。发明人还意料不到地发现，采用含有苯基的有机硅有利于降低封装树脂的加工粘度，使封装操作更易进行，通常情况下苯基易被氧化形成醌，材料因此变黄，然而苯基的位阻效应能够降低分子链间的相互作用力，增加分子链的迁移性能，因此为了平衡材料的操作性和耐UV性能，需将预聚体的原料用量比例控制在一定范围内。
本发明中的铂金催化剂用于催化硅氢键与双键之间的加成反应，可为市售，例如卡斯特铂催化剂。
在一些优选的实施方式中，所述(C)铂金催化剂的用量为(A)具有如式1所示结构的化合物的0.05～1wt％；进一步优选的，所述(C)铂金催化剂的用量为(A)具有如式1所示结构的化合物的0.1～0.5wt％。
从调节反应程度的角度考虑，在一些优选的实施方式中，所述预聚体的制备原料还包括(D)抑制剂。
本发明中的抑制剂用于降低化学反应速度，其种类不作特殊限定，可为本领域技术人员熟知的任何一中，例如马来酸酯抑制剂、富马酸酯抑制剂、有机膦类抑制剂、炔类抑制剂等。
在一些优选的实施方式中，所述抑制剂选自3，7，11-三甲基十二炔-3-醇(CAS号：1604-35-9，简称TMDO)、3，5-二甲基-1-己炔-3-醇、3，6-二甲基-1-庚炔-3-醇、富马酸二乙酯、乙炔环己醇(CAS号：78-27-3)、甲基丁炔醇(CAS号：115-19-5)、马来酸甲酯中的一种或多种的混合。
在一些优选的实施方式中，所述(D)抑制剂的用量为(A)具有如式1所 示结构的化合物的0～0.1wt％，0除外；进一步优选的，所述(D)抑制剂的用量为(A)具有如式1所示结构的化合物的0.01～0.05wt％。
本发明的第二方面提供了上述预聚体的制备方法，包括以下步骤：将100重量份(A)具有如式1所示结构的化合物与(B)含有苯基和Si-H基团的有机硅氧烷、(D)抑制剂在60～150℃下融化，混合均匀后降温至60～120℃，加入(C)铂金催化剂，搅拌5～15h，得到预聚体。
本发明的第三方面提供了一种封装树脂，其制备原料包括：环氧树脂、如上所述的预聚体、固化剂、粘接力促进剂、催化剂。
从提高环氧树脂与预聚体的相容性角度考虑，在一些优选的实施方式中，所述环氧树脂选自三环氧丙基异氰尿酸酯(TGIC，CAS号：2451-62-9)、脂环族环氧树脂(CAS号：3130-19-6)、氢化双酚A环氧树脂中的一种或多种的混合；进一步优选的，所述环氧树脂为三环氧丙基异氰尿酸酯和/或脂环族环氧树脂。
从平衡封装树脂的操作性能和耐UV性能角度考虑，在一些优选的实施方式中，所述环氧树脂与预聚体的重量比为(3～20)∶1；进一步优选的，所述环氧树脂与预聚体的重量比为(4～10)∶1。
在一些优选的实施方式中，所述固化剂为酸酐固化剂；进一步优选的，所述酸酐固化剂选自邻苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸二酐、氢化均苯四甲酸二酐、顺丁烯二酸酐、四氢苯二甲酸酐、甲基四氢苯二甲酸酐、六氢苯二甲酸酐、甲基六氢苯二甲酸酐、桐油酸酐、十二烯基丁二酸酐、纳迪克酸酐、甲基纳迪克酸酐、戊二酸酐、氢化甲基纳迪克酸酐、甲基环己烯四羧酸二酐、聚壬二酸酐、聚癸二酸酐、1，4，5，6-四溴苯二甲酸酐中的一种或多种的混合。
在一些优选的实施方式中，所述酸酐固化剂的用量按酸酐基团含量与体系环氧基团含量的摩尔比为(0.8～1)∶1计算得到。本文中所述体系环氧基团含量为环氧树脂与预聚体中的环氧基团含量之和。
在一些优选的实施方式中，所述粘接力促进剂选自γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二乙氧基硅烷、γ-(2，3-环氧丙氧)丙基三乙氧基硅烷、γ-(2，3-环氧丙氧)丙基甲基二甲氧基硅烷、β-(3，4-环氧环己基)乙基三甲氧基硅烷、3-巯丙基三甲氧基硅烷、3-巯丙基三乙氧基硅烷、2，4，6，8-四[2-(3，4-环氧环己基乙基)四甲基环四硅氧烷、2，4，6-三[2-(3，4-环氧环己基乙基)]四甲基环四硅氧烷、 二[2-(3，4-环氧环己基乙基)]四甲基环四硅氧烷、2，4，6，8-四甲基-[2-(3，4-环氧环己基乙基)]环四硅氧烷、2，4，6，8-四甲基-2，4，6，8-四[3-(环氧乙烷基甲氧基)丙基]环四硅氧烷、2，4，6，8-四甲基-2-[3-(环氧乙烷基甲氧基)丙基]环四硅氧烷中的一种或多种的混合。
在一些优选的实施方式中，所述粘接力促进剂的用量为环氧树脂与预聚体总量的0.01～5wt％；进一步优选的，所述粘接力促进剂的用量为环氧树脂与预聚体总量的0.05～3wt％。
在一些优选的实施方式中，所述催化剂选自三苯基膦、甲基三辛基鏻二甲基磷酸盐、四丁基鏻乙酸盐、甲基三丁基鏻二甲基磷酸盐、苄基三苯基鏻氯化物、四丁基鏻氯化物、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、苯并咪唑中的一种或多种的混合。
在一些优选的实施方式中，所述催化剂的用量为环氧树脂、预聚体、固化剂总量的0.01～5wt％；进一步优选的，所述催化剂的用量为环氧树脂、预聚体、固化剂总量的0.1～1wt％。
在一些优选的实施方式中，所述封装树脂的制备原料还包括颜料、无机填料、抗氧剂、抗紫外吸收剂中的至少一种。
作为颜料，可举例二氧化钛、炭黑等，添加量可为环氧树脂、预聚体、固化剂总量的1～400wt％；作为无机填料，可举例二氧化硅、氧化铝、碳酸钙、高岭土等，添加量可为环氧树脂、预聚体、固化剂总量的50～800wt％；作为抗氧剂，可举例2，6-二叔丁基-4-甲基苯酚、抗氧剂1010、抗氧剂1076等，添加量可为环氧树脂、预聚体、固化剂总量的0.01～5wt％；作为抗紫外吸收剂，可举例UV-326、UV-531、UV-234、UV-320等，添加量可为环氧树脂、预聚体、固化剂总量的0.01～5wt％。
本发明的第四方面提供了上述封装树脂的制备方法，包括以下步骤：取环氧树脂、如上所述的预聚物，在150～200℃下搅拌，再降温至100～150℃，加入固化剂、粘接力促进剂、催化剂，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
本发明的第五方面提供了一种白色反射杯用封装树脂，其制备原料包括100重量份上述封装树脂、50～400重量份二氧化钛。
本发明的第六方面提供了一种如上所述的白色反射杯用封装树脂的应用，其 用于功率为1～3W的白光LED器件。
本发明的第七方面提供了一种黑色反射杯用封装树脂，其制备原料包括100重量份上述封装树脂、1～30重量份炭黑。
本发明的第八方面提供了一种如上所述的黑色反射杯用封装树脂的应用，其用于户外RGB显示屏的表贴SMT发光器件。
本发明的第九方面提供了一种LED器件，其由金属框架或树脂基板与上述封装树脂通过注塑得到反射杯结构。本发明中所述反射杯既是以液体灌封胶浇注封装LED时的载体，又是构成LED单面出光的反射材料，该反射杯由上述封装树脂成型制成，可提升LED器件的耐热性和耐光老化性能。
实施例
下面通过实施例对本发明进行具体描述。有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。
实施例1
实施例1提供了一种预聚体，将100重量份DA-MGIC(二烯丙基单缩水甘油基异氰脲酸酯，CAS号：20395-16-8)与RH-SH309(苯基含氢有机硅氧烷，氢含量0.87％，购自宁波润禾高新材料科技股份有限公司)、0.05重量份3，7，11-三甲基十二炔-3-醇(CAS号：1604-35-9，简称TMDO)在100℃下融化0.5h，混合均匀后降温至90℃加入0.5重量份PT5000(铂金催化剂，浓度5000ppm，购自深圳市科骏驰科技有限公司)，搅拌10h，得到预聚体。
本例中按照RH-SH309中SiH含量与DA-MGIC中乙烯基含量摩尔比为0.95∶1计算得到的RH-SH309的用量。
实施例2
实施例2提供了一种预聚体，将100重量份MA-DGIC(单烯丙基二缩水甘油基异氰脲酸酯，CAS号：69731-45-9)与RH-SH309(苯基含氢有机硅氧烷，氢含量0.87％，购自宁波润禾高新材料科技股份有限公司)、0.05重量份3，7，11-三甲基十二炔-3-醇(CAS号：1604-35-9，简称TMDO)在100℃下融化0.5h，混合均匀后降温至90℃加入0.5重量份PT 5000(铂金催化剂，浓度5000ppm，购自深圳市科骏驰科技有限公司)，搅拌10h，得到预聚体。
本例中按照RH-SH309中SiH含量与MA-DGIC中乙烯基含量摩尔比为0.95∶1计算得到的RH--SH309的用量。
实施例3
实施例3提供了一种预聚体，将100重量份MA-DGIC(单烯丙基二缩水甘油基异氰脲酸酯，CAS号：69731-45-9)与RH-SH309(苯基含氢有机硅氧烷，氢含量0.87％，购自宁波润禾高新材料科技股份有限公司)、0.05重量份3，7，11-三甲基十二炔-3-醇(CAS号：1604-35-9，简称TMDO)在90℃下融化0.5h，混合均匀后降温至80℃加入0.5重量份PT 5000(铂金催化剂，浓度5000ppm，购自深圳市科骏驰科技有限公司)，搅拌8h，得到预聚体。
本例中按照RH-SH309中SiH含量与MA-DGIC中乙烯基含量摩尔比为0.5∶1计算得到的RH-SH309的用量。
实施例4
实施例4提供了一种预聚体，将100重量份DA-MGIC(二烯丙基单缩水甘油基异氰脲酸酯，CAS号：20395-16-8)与RH-SH309(苯基含氢有机硅氧烷，氢含量0.87％，购自宁波润禾高新材料科技股份有限公司)、0.05重量份3，7，11-三甲基十二炔-3-醇(CAS号：1604-35-9，简称TMDO)在90℃下融化0.5h，混合均匀后降温至80℃加入0.5重量份PT 5000(铂金催化剂，浓度5000ppm，购自深圳市科骏驰科技有限公司)，搅拌8h，得到预聚体。
本例中按照RH-SH309中SiH含量与DA-MGIC中乙烯基含量摩尔比为0.25∶1计算得到的RH-SH309的用量。
实施例5
实施例5提供了一种预聚体，将100重量份DA-MGIC(二烯丙基单缩水甘油基异氰脲酸酯，CAS号：20395-16-8)与XL-2460(苯基含氢有机硅氧烷，SiH含量：3.85mmol/g，购自安必亚特种有机硅(南通)有限公司)、0.05重量份3，7，11-三甲基十二炔-3-醇(CAS号：1604-35-9，简称TMDO)在90℃下融化0.5h，混合均匀后降温至80℃加入0.1重量份PT 5000(铂金催化剂，浓度5000ppm，购自深圳市科骏驰科技有限公司)，搅拌6h，得到预聚体。
本例中按照XL-2460中SiH含量与DA-MGIC中乙烯基含量摩尔比为0.5∶1计算得到的XL-2460的用量。
实施例6
实施例6提供了一种预聚体，将100重量份DA-MGIC(二烯丙基单缩水甘油基异氰脲酸酯，CAS号：20395-16-8)与XL-2460(苯基含氢有机硅氧烷，SiH含量：3.85mmol/g，购自安必亚特种有机硅(南通)有限公司)、0.05重量份3，7，11-三甲基十二炔-3-醇(CAS号：1604-35-9，简称TMDO)在90℃下融化0.5h，混合均匀后降温至80℃加入0.1重量份PT 5000(铂金催化剂，浓度5000ppm，购自深圳市科骏驰科技有限公司)，搅拌6h，得到预聚体。
本例中按照XL-2460中SiH含量与DA-MGIC中乙烯基含量摩尔比为0.95∶1计算得到的XL-2460的用量。
实施例7
实施例7提供了一种预聚体，将100重量份DA-MGIC(二烯丙基单缩水甘油基异氰脲酸酯，CAS号：20395-16-8)与XL-2460(苯基含氢有机硅氧烷，SiH含量：3.85mmol/g，购自安必亚特种有机硅(南通)有限公司)、0.05重量份3，7，11-三甲基十二炔-3-醇(CAS号：1604-35-9，简称TMDO)在90℃下融化0.5h，混合均匀后降温至80℃加入0.1重量份PT 5000(铂金催化剂，浓度5000ppm，购自深圳市科骏驰科技有限公司)，搅拌6h，得到预聚体。
本例中按照XL-2460中SiH含量与DA-MGIC中乙烯基含量摩尔比为0.25∶1计算得到的XL-2460的用量。
实施例8
实施例8提供了一种预聚体，将100重量份MA-DGIC(单烯丙基二缩水甘油基异氰脲酸酯，CAS号：69731-45-9)与XL-2460(有机硅氧烷，SiH含量：3.85mmol/g，购自安必亚特种有机硅(南通)有限公司)、0.05重量份3，7，11-三甲基十二炔-3-醇(CAS号：1604-35-9，简称TMDO)在90℃下融化0.5h，混合均匀后降温至80℃加入0.1重量份PT 5000(铂金催化剂，浓度5000ppm，购自深圳市科骏驰科技有限公司)，搅拌6h，得到预聚体。
本例中按照XL-2460中SiH含量与MA-DGIC中乙烯基含量摩尔比为0.5∶1计算得到的XL-2460的用量。
发明人在实施例1～8的对比中发现，相同实验条件下，DA-MGIC与有机硅氧烷的反应相比于MA-DGIC与有机硅的反应更易进行，XL-2460参与的反应相比于RH309参与的反应更易进行。上述反应进行的难易程度根据反应时间长短、反应温度高低判断，若反应时间长、反应温度高，则操作性不好，操作性的 评价结果按照由易到难的顺序依次分为优异、良好、差，实施例1～8的操作性和收率(使用滴定法测试环氧当量)见表1。
表1
实施例 操作性 收率
实施例1 差 55％
实施例2 差 50％
实施例3 良好 65％
实施例4 良好 70％
实施例5 优异 95％
实施例6 优异 90％
实施例7 优异 95％
实施例8 优异 85％
实施例9
实施例9提供了一种封装树脂，取90重量份三环氧丙基异氰尿酸酯(TGIC，CAS号：2451-62-9)、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、10重量份实施例2中的预聚物，在180℃下搅拌0.5h，降温至130℃，加入150重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.05重量份3-巯丙基三甲氧基硅烷(CAS号：4420-74-0)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
实施例10
实施例10提供了一种封装树脂，取90重量份三环氧丙基异氰尿酸酯(TGIC，CAS号：2451-62-9)、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、10重量份实施例4中的预聚物，在180℃下搅拌0.5h，降温至130℃，加入150重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.25重量份γ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷(CAS号：14513-34-9)、0.25重量份γ-(2，3-环氧丙氧)丙基甲基二甲氧基硅烷(CAS号：65799-47-5)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
实施例11
实施例11提供了一种封装树脂，取90重量份三环氧丙基异氰尿酸酯(TGIC，CAS号：2451-62-9)、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、 10重量份实施例6中的预聚物，在150℃下搅拌0.5h，降温至130℃，加入150重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.25重量份γ-(2，3-环氧丙氧)丙基三乙氧基硅烷(CAS号：2602-34-8)、0.25重量份γ-甲基丙烯酰氧基丙基甲基二乙氧基硅烷(CAS号：65100-04-1)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
实施例12
实施例12提供了一种封装树脂，取90重量份三环氧丙基异氰尿酸酯(TGIC，CAS号：2451-62-9)、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、10重量份实施例7中的预聚物，在180℃下搅拌0.5h，降温至130℃，加入150重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、1重量份β-(3，4-环氧环己基)乙基三甲氧基硅烷(CAS号：3388-04-3)、1重量份2，4，6，8-四[2-(3，4-环氧环己基乙基)]四甲基环四硅氧烷(CAS号：121225-98-7)、1重量份3-巯丙基三乙氧基硅烷(CAS号：14814-09-6)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
实施例13
实施例13提供了一种封装树脂，取90重量份三环氧丙基异氰尿酸酯(TGIC，CAS号：2451-62-9)、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、10重量份实施例8中的预聚物，在180℃下搅拌0.5h，降温至130℃，加入150重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.05重量份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(CAS号：2530-85-0)、0.05重量份2，4，6，8-四[2-(3，4-环氧环己基乙基)]四甲基环四硅氧烷(CAS号：121225-98-7)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
实施例14
实施例14提供了一种封装树脂，取85重量份三环氧丙基异氰尿酸酯(TGIC，CAS号：2451-62-9)、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、15重量份实施例7中的预聚物，在180℃下搅拌0.5h，降温至130℃，加入130重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.025重量份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(CAS号：2530-85-0)、0.05重量份2，4，6，8-四甲基-2，4，6，8-四[3-(环氧乙烷基甲氧基)丙基]环四硅氧烷(CAS号：60665-85-2)、0.5 重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
实施例15
实施例15提供了一种封装树脂，取80重量份三环氧丙基异氰尿酸酯(TGIC，CAS号：2451-62-9)、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、20重量份实施例7中的预聚物，在180℃下搅拌0.5h，降温至130℃，加入110重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.05重量份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(CAS号：2530-85-0)、0.05重量份2，4，6，8-四甲基-2-[3-(环氧乙烷基甲氧基)丙基]环四硅氧烷(CAS号：61614-55-9)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
实施例16
实施例16提供了一种封装树脂，取90重量份脂环族环氧树脂A(双(7-氧杂双环[4.1.0]3-庚甲基)乙二酸酯)、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、10重量份实施例2中的预聚物，在180℃下搅拌0.5h，降温至130℃，加入110重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.025重量份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(CAS号：2530-85-0)、0.025重量份γ-甲基丙烯酰氧基丙基甲基二乙氧基硅烷(CAS号：65100-04-1)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
实施例17
实施例17提供了一种封装树脂，取90重量份脂环族环氧树脂A、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、10重量份实施例4中的预聚物，在180℃下搅拌0.5h，降温至130℃，加入110重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.025重量份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(CAS号：2530-85-0)、0.025重量份γ-甲基丙烯酰氧基丙基甲基二乙氧基硅烷(CAS号：65100-04-1)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
实施例18
实施例18提供了一种封装树脂，取90重量份脂环族环氧树脂A、0.05重量 份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、10重量份实施例7中的预聚物，在180℃下搅拌0.5h，降温至130℃，加入110重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.025重量份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(CAS号：2530-85-0)、0.025重量份γ-甲基丙烯酰氧基丙基甲基二乙氧基硅烷(CAS号：65100-04-1)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
实施例19
实施例19提供了一种封装树脂，取90重量份脂环族环氧树脂A、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)、10重量份实施例8中的预聚物，在180℃下搅拌0.5h，降温至130℃，加入110重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.025重量份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(CAS号：2530-85-0)、0.025重量份γ-甲基丙烯酰氧基丙基甲基二乙氧基硅烷(CAS号：65100-04-1)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
对比例1
对比例1提供了一种封装树脂，取90重量份三环氧丙基异氰尿酸酯(TGIC，CAS号：2451-62-9)、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)，在180℃下搅拌0.5h，降温至130℃，加入150重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.05重量份3-巯丙基三甲氧基硅烷(CAS号：4420-74-0)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
对比例2
对比例2提供了一种封装树脂，取90重量份脂环族环氧树脂A、0.05重量份2，6-二叔丁基-4-甲基苯酚(CAS号：2409-55-4)，在180℃下搅拌0.5h，降温至130℃，加入110重量份六氢化邻苯甲酸二酐(CAS号：85-42-7)、0.025重量份γ-甲基丙烯酰氧基丙基三甲氧基硅烷(CAS号：2530-85-0)、0.025重量份γ-甲基丙烯酰氧基丙基甲基二乙氧基硅烷(CAS号：65100-04-1)、0.5重量份2-乙基-4-甲基咪唑(CAS号：931-36-2)，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
对实施例9～19、对比例1～2的操作性进行评价，使用各实施例中的封装 树脂对芯片进行包封，若封装树脂不能对芯片包封，或者熔融粘度过大，则操作性不好，操作性的评价结果按照从好到差的顺序依次分为优异、较好、差，实施例9～19、对比例1～2的操作性见表2。
对实施例9～19、对比例1～2的透明性进行评价，将封装树脂预热，挤压入模腔，160℃模压固化300s，再在150～170℃固化2～4小时，得到厚度均匀(200±10um)的测试样片，观察模压的样片是否透明或乳白，透明性的评价结果按照透明、半透明、乳白的顺序依次分为优异、较好、差，实施例9～19、对比例1～2的透明性见表2。
对实施例9～19、对比例1～2的耐UV性能进行评价，将上述模压样片作为测试样本统一放入UV照射机，使用色差仪测试照射1h后的颜色对比老化状态，b值越大，耐UV光衰越差，结果见表2。
表2
实施例 操作性 透明性 耐UV性能 UV测试后b
实施例9 优异 差 优异 5-6
实施例10 优异 优异 较好 6-7
实施例11 优异 优异 较好 6-7
实施例12 较好 较好 较好 6-7
实施例13 较好 较好 较好 6-7
实施例14 优异 较好 较好 6-7
实施例15 优异 较好 较好 6-7
实施例16 优异 优异 优异 5-6
实施例17 优异 优异 较好 7-9
实施例18 优异 优异 较好 7-9
实施例19 优异 优异 较好 7-9
对比例1 优异 较好 良好 6-7
对比例2 优异 优异 良好 7-8
实施例9和对比例1、实施例16和对比例2经UV灯耐蓝光光衰测试发现，添加了本发明所述的预聚物后得到的封装树脂具有更好的耐UV光衰性能，该效果通过图1、2可知。
发明人在研发过程中根据大量实验结果发现，在三环氧丙基异氰尿酸酯体系中，实施例1～8中任意选择一个实施例，按照实施例9的条件，可以得到性能优异的封装树脂，用其封装LED芯片，能够得到具有耐蓝光性能的LED白光芯片。
发明人在研发过程中根据大量实验结果发现，在脂环族环氧树脂体系中，实施例1～8中任意选择一个实施例，按照实施例16的条件，可以得到性能优异的封装树脂，用其封装LED芯片，能够得到具有耐蓝光性能的LED白光芯片。
前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (10)

  1. 一种预聚体，其特征在于，所述预聚体的制备原料包括：
    (A)具有如式1所示结构的化合物，式1：
    Figure PCTCN2021126349-appb-100001
    其中R 1、R 2、R 3分别独立地选自乙烯基或环氧基；
    (B)含有苯基和Si-H基团的有机硅氧烷；
    (C)铂金催化剂。
  2. 如权利要求1所述的预聚体，其特征在于，所述预聚体的制备原料还包括(D)抑制剂。
  3. 一种如权利要求2所述的预聚体的制备方法，其特征在于，包括以下步骤：将100重量份(A)具有如式1所示结构的化合物与(B)含有苯基和Si-H基团的有机硅氧烷、(D)抑制剂在60～150℃下融化，混合均匀后降温至60～120℃，加入(C)铂金催化剂，搅拌5～15h，得到预聚体。
  4. 一种封装树脂，其特征在于，所述封装树脂的制备原料包括环氧树脂、如权利要求1或2所述的预聚体、固化剂、粘接力促进剂、催化剂。
  5. 一种如权利要求4所述的封装树脂的制备方法，其特征在于，包括以下步骤：取环氧树脂、预聚物，在150～200℃下搅拌，再降温至100～150℃，加入固化剂、粘接力促进剂、催化剂，搅拌，出料，冷却，粉碎，打饼，得到封装树脂。
  6. 一种白色反射杯用封装树脂，其特征在于，其制备原料包括100重量份如权利要求4所述的封装树脂、50～400重量份二氧化钛。
  7. 一种如权利要求6所述的白色反射杯用封装树脂的应用，其特征在于，其用于功率为1～3W的白光LED器件。
  8. 一种黑色反射杯用封装树脂，其特征在于，其制备原料包括100重量份如权利要求4所述的封装树脂、1～30重量份炭黑。
  9. 一种如权利要求8所述的黑色反射杯用封装树脂的应用，其特征在于，其用于户外RGB显示屏的表贴SMT发光器件。
  10. 一种LED器件，其特征在于，其由金属框架或树脂基板与如权利要求4所述的封装树脂通过注塑得到反射杯结构。
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