CN108192284B - High-temperature yellowing resistant transparent epoxy molding compound and preparation method thereof - Google Patents
High-temperature yellowing resistant transparent epoxy molding compound and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08L2203/20—Applications use in electrical or conductive gadgets
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Abstract
The transparent epoxy molding compound with high temperature yellowing resistance is characterized by being prepared from the following raw materials in parts by weight: 31-60% of alicyclic epoxy resin, 30-50% of phthalic anhydride curing agent, 2-5% of alcohol ring-opening agent, 0.1-1% of phosphorus-containing accelerator, 0.1-1% of hindered phenol antioxidant, 0.01-0.05% of auxiliary antioxidant, 0.1-1% of silane coupling agent, 0.1-1% of mold release agent and 2-10% of hydroxyl-terminated hyperbranched resin. The invention also provides a preparation method of the high-temperature yellowing resistant transparent epoxy molding compound. The transparent epoxy molding compound disclosed by the invention is high in light transmittance, good in high-temperature yellowing resistance, higher in glass transition temperature and excellent in bending resistance and shearing resistance, can meet the performance requirements of LED packaging, and can be particularly applied to the packaging of small-spacing full-color LEDs to meet the performance requirements of full-color LED packaging.
Description
Technical Field
The invention relates to a packaging material applied to an LED, in particular to a high-temperature yellowing resistant transparent epoxy molding compound and a preparation method thereof.
Background
The epoxy molding compound has the advantages of high reliability, low cost, simple production process, suitability for large-scale production and the like, is widely applied to the microelectronic packaging industry, and has the functions of mechanical support and heat dissipation besides protecting the chip from external dust, moisture, ions, radiation and mechanical impact.
The traditional epoxy molding compound mostly adopts an o-cresol formaldehyde epoxy-phenolic resin system, is added with a filler and a coloring agent, and the cured resin is mostly opaque and black, and due to the benzene ring structure in the o-cresol formaldehyde epoxy resin, the yellowing phenomenon is easy to occur in a long-term high-temperature environment, so that the epoxy molding compound cannot be applied to the field of optical LED packaging.
The Chinese patent application publication No. CN105504674A discloses an epoxy molding compound for an LED packaging bracket, and a preparation method and application thereof, wherein the epoxy molding compound is composed of purified epoxy resin, a curing agent, a curing accelerator, an inorganic filler, a light reflection regulator and a flame retardant, and the prepared epoxy molding compound has the advantages of high heat conductivity, high heat resistance, UV resistance, low thermal expansion coefficient and the like. The Chinese patent application publication No. CN102408676A discloses an environment-friendly epoxy molding compound applied to the field of electronic packaging high polymer materials and a preparation method thereof, wherein the epoxy molding compound comprises epoxy resin, phenolic resin, filler, carbon black, a curing accelerator and the like, and the prepared epoxy molding compound is environment-friendly and harmless. However, the molding compound after being molded by the two molding compounds has low transmittance and poor high-temperature yellowing resistance, and is difficult to meet the requirements of optical LED packaging.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-temperature yellowing resistant transparent epoxy molding compound and a preparation method thereof, wherein the transparent epoxy molding compound has high light transmittance and good high-temperature yellowing resistance, has higher glass transition temperature and excellent bending resistance and shearing resistance, and can meet the performance requirements of LED packaging. The technical scheme is as follows:
the transparent epoxy molding compound with high temperature yellowing resistance is characterized by being prepared from the following raw materials in parts by weight: 31-60% of alicyclic epoxy resin, 30-50% of phthalic anhydride curing agent, 2-5% of alcohol ring-opening agent, 0.1-1% of phosphorus-containing accelerator, 0.1-1% of hindered phenol antioxidant, 0.01-0.05% of auxiliary antioxidant, 0.1-1% of silane coupling agent, 0.1-1% of mold release agent and 2-10% of hydroxyl-terminated hyperbranched resin.
Preferably, the alicyclic epoxy resin is one or a mixture of more of poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3:1), diglycidyl cyclohexane-1, 2-dicarboxylate, diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate and 4-vinyl-1-cyclohexene diepoxide. The alicyclic epoxy resin is solid or liquid, and the epoxy equivalent is 160-200. Compared with the novolac epoxy resin commonly used in the traditional epoxy molding compound, the alicyclic epoxy resin has the following advantages: (1) the epoxy equivalent is small, the crosslinking density is large, and the structure contains a rigid structure with good thermal stability, so that the heat resistance is good; (2) the paint does not contain benzene rings, so that the paint has good ultraviolet resistance and weather resistance; (3) the synthesis process does not contain Cl, Na and other ions, so that the electrical property is good, and particularly the high-temperature electrical property and the arc resistance are good.
Preferably, the above-mentioned phthalic anhydride curing agent is one or a mixture of both of 4-methylhexahydrophthalic anhydride and 4-methyltetrahydrophthalic anhydride.
Preferably, the alcohol ring-opener is one or a mixture of two of ethylene glycol, glycerol and pentaerythritol. The alcohol ring-opener helps to assist the ring opening of the anhydride, so that the generated carboxylic acid groups further react with the epoxy groups to form a compact cross-linked structure.
Preferably, the above-mentioned phosphorus-containing accelerator is one or a mixture of triphenylmethyl phosphonium bromide and triphenylethyl phosphonium bromide. The accelerant is colorless transparent solid particles, and is easily soluble in the phthalic anhydride curing agent at a high temperature.
Preferably, the hindered phenol-based antioxidant is one or a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate. The epoxy resin is easy to generate yellowing phenomenon after being placed in a high-temperature environment for a long time, and the thermal yellowing phenomenon of the epoxy resin can be effectively reduced by adding the hindered phenol antioxidant.
Preferably, the auxiliary antioxidant is one or a mixture of trisnonylphenyl phosphite and tris [2, 4-di-tert-butylphenyl ] phosphite.
Preferably, the silane coupling agent is one or a mixture of gamma-glycidoxypropyltrimethoxysilane and gamma-aminopropyltriethoxysilane.
Preferably, the release agent is one or a mixture of zinc stearate and magnesium stearate.
The hydroxyl-terminated hyperbranched resin is used as a toughening agent, the outer end of the structure of the resin contains a large amount of hydroxyl groups, the reaction activity is high, and the bending resistance and the shearing resistance of the epoxy resin can be effectively improved. The structural formula of the hydroxyl-terminated hyperbranched resin is preferably one of the following structural formulas (1) to (3):
（1）
（2）
（3）
the invention also provides a preparation method of the high-temperature yellowing resistant transparent epoxy molding compound, which is characterized by comprising the following steps:
(1) the following raw materials are prepared by weight: 31-60% of alicyclic epoxy resin, 30-50% of phthalic anhydride curing agent, 2-5% of alcohol ring-opening agent, 0.1-1% of phosphorus-containing accelerator, 0.1-1% of hindered phenol antioxidant, 0.01-0.05% of auxiliary antioxidant, 0.1-1% of silane coupling agent, 0.1-1% of mold release agent and 2-10% of hydroxyl-terminated hyperbranched resin;
(2) adding alicyclic epoxy resin and hydroxyl-terminated hyperbranched resin into a clean and dry stirring tank A with a heating device, heating to 110 ℃ at 100-;
(3) adding a phthalic anhydride curing agent, an alcohol ring-opening agent, a phosphorus-containing promoter, a hindered phenol antioxidant, an auxiliary antioxidant, a silane coupling agent and a release agent into a clean and dry stirring tank B, and stirring at the stirring speed of 300-500 r/min for 5-20 min (stirring at normal temperature) to obtain a first mixed solution;
(4) introducing the first mixed solution in the stirring tank B into the stirring tank A through a conduit, and stirring at the temperature of 100-110 ℃ (namely heating the material in the stirring tank A to keep the temperature at 100-110 ℃), wherein the stirring speed is 300-500 r/min, and the stirring time is 5-15 min, so as to obtain a second mixed solution;
(5) adding the second mixed solution into an extruder (such as a double-screw extruder) through a feed hopper for extrusion, cooling to 20-30 ℃ to obtain the flaky high-temperature yellowing resistant transparent epoxy molding compound (the material extruded by the extruder can be cooled by adopting methods such as tape casting, calendaring and the like to form flaky material), crushing the flaky high-temperature yellowing resistant transparent epoxy molding compound into granules, grinding the granules into powder material, and demagnetizing the powder material to obtain the powdery high-temperature yellowing resistant transparent epoxy molding compound. The obtained powdery transparent epoxy molding compound with high temperature yellowing resistance can be pressed into a cake shape for storage, transportation and use.
The transparent epoxy molding compound disclosed by the invention is high in light transmittance, good in high-temperature yellowing resistance (after aging at the high temperature of 150 ℃ for 500 hours, the color of a molding compound product does not change obviously), higher in glass transition temperature and excellent in bending resistance and shearing resistance, and capable of meeting the performance requirements of LED packaging, especially being applied to the packaging of small-spacing full-color LEDs and meeting the performance requirements of full-color LED packaging.
Detailed Description
Example 1
In this embodiment, the preparation method of the transparent epoxy molding compound with high temperature yellowing resistance comprises the following steps:
(1) the following raw materials are prepared by weight: alicyclic epoxy resin 51.18% (wherein cyclohexane-1, 2-dicarboxylic acid diglycidyl ester 41.18%, 4-vinyl-1-cyclohexene diepoxide 10%), phthalic anhydride curing agent 36.8% (both 4-methyl hexahydrophthalic anhydride), alcohol ring-opener 4% (both glycerol), phosphorus-containing accelerator 0.2% (both triphenyl methyl phosphonium bromide), hindered phenol antioxidant 0.5% (both beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate), auxiliary antioxidant 0.02% (both trinonyl phenyl phosphite), silane coupling agent 0.5% (both gamma-aminopropyl triethoxysilane), release agent 0.8% (both zinc stearate), and hydroxyl-terminated hyperbranched resin 6%;
(2) adding the alicyclic epoxy resin and the hydroxyl-terminated hyperbranched resin into a clean and dry stirring tank A with a heating device, heating to 100 ℃ (namely heating the material in the stirring tank A to 100 ℃), and stirring for 10 minutes at a stirring speed of 500 revolutions per minute;
(3) adding a phthalic anhydride curing agent, an alcohol ring-opening agent, a phosphorus-containing accelerator, a hindered phenol antioxidant, an auxiliary antioxidant, a silane coupling agent and a mold release agent into a clean and dry stirring tank B, and stirring at a stirring speed of 500 revolutions per minute for 10 minutes (stirring at normal temperature) to obtain a first mixed solution;
(4) introducing the first mixed solution in the stirring tank B into the stirring tank A through a conduit, and stirring at the temperature of 100 ℃ (namely heating the material in the stirring tank A to keep the temperature at 100 ℃), wherein the stirring speed is 500 revolutions per minute, and the stirring time is 10 minutes to obtain a second mixed solution;
(5) and adding the second mixed solution into a double-screw extruder through a feed hopper for extrusion, cooling to 20 ℃ to obtain the flaky high-temperature yellowing resistant transparent epoxy molding compound (the material extruded by the extruder can be cooled by adopting methods such as tape casting, calendaring and the like to form flaky material), crushing the flaky high-temperature yellowing resistant transparent epoxy molding compound into granules, grinding the granules into powder, and demagnetizing the powder to obtain the powdery high-temperature yellowing resistant transparent epoxy molding compound.
The obtained powdery transparent epoxy molding compound with high temperature yellowing resistance can be pressed into a cake shape for storage, transportation and use.
The structural formula of the hydroxyl-terminated hyperbranched resin is as follows:
example 2
In this embodiment, the preparation method of the transparent epoxy molding compound with high temperature yellowing resistance comprises the following steps:
(1) the following raw materials are prepared by weight: 53.35% of alicyclic epoxy resin (all poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propylene glycol ether (3: 1)), 38.2% of phthalic anhydride curing agent (all 4-methyl hexahydrophthalic anhydride), 2% of alcohol ring-opening agent (all pentaerythritol), 0.4% of phosphorus-containing accelerator (0.2% of triphenylmethyl phosphonium bromide and 0.2% of triphenylethyl phosphonium bromide), 0.5% of hindered phenol antioxidant (all beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate), 0.05% of auxiliary antioxidant (all tris [ 2.4-di-tert-butylphenyl ] phosphite), 1% of silane coupling agent (all gamma-glycidyl ether oxypropyltrimethoxysilane), 0.5 percent of release agent (magnesium stearate) and 4 percent of hydroxyl-terminated hyperbranched resin;
(2) adding the alicyclic epoxy resin and the hydroxyl-terminated hyperbranched resin into a clean and dry stirring tank A with a heating device, heating to 110 ℃ (namely heating the material in the stirring tank A to 110 ℃), and stirring for 10 minutes at a stirring speed of 400 revolutions per minute;
(3) adding a phthalic anhydride curing agent, an alcohol ring-opening agent, a phosphorus-containing accelerator, a hindered phenol antioxidant, an auxiliary antioxidant, a silane coupling agent and a release agent into a clean and dry stirring tank B, and stirring at a stirring speed of 500 revolutions per minute for 15 minutes (stirring at normal temperature) to obtain a first mixed solution;
(4) introducing the first mixed solution in the stirring tank B into the stirring tank A through a conduit, and stirring at the temperature of 110 ℃ (namely heating the material in the stirring tank A to keep the temperature at 110 ℃), wherein the stirring speed is 500 revolutions per minute, and the stirring time is 8 minutes, so as to obtain a second mixed solution;
(5) and adding the second mixed solution into a double-screw extruder through a feed hopper for extrusion, cooling to 30 ℃ to obtain the flaky high-temperature yellowing resistant transparent epoxy molding compound (the material extruded by the extruder can be cooled by adopting methods such as tape casting, calendaring and the like to form flaky material), crushing the flaky high-temperature yellowing resistant transparent epoxy molding compound into granules, grinding the granules into powder, and demagnetizing the powder to obtain the powdery high-temperature yellowing resistant transparent epoxy molding compound.
The obtained powdery transparent epoxy molding compound with high temperature yellowing resistance can be pressed into a cake shape for storage, transportation and use.
The hydroxyl-terminated hyperbranched resin has the following structure:
example 3
In this embodiment, the preparation method of the transparent epoxy molding compound with high temperature yellowing resistance comprises the following steps:
(1) the following raw materials are prepared by weight: alicyclic epoxy resin 45.48% (wherein cyclohexane-1, 2-dicarboxylic acid diglycidyl ester 31.84%, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester 13.64%), phthalic anhydride curing agent 37.4% (wherein 4-methyltetrahydrophthalic anhydride), alcohol ring-opening agent 5% (wherein ethylene glycol 3%, glycerol 2%), phosphorus-containing accelerator 0.1% (wherein triphenyl ethyl phosphonium bromide), hindered phenol antioxidant 0.5% (wherein beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate), auxiliary antioxidant 0.02% (wherein tris [ 2.4-di-tert-butylphenyl ] phosphite), silane coupling agent 1% (wherein gamma-glycidyl ether oxypropyltrimethoxysilane) and mold release agent 0.5% (wherein magnesium stearate), 10% of hydroxyl-terminated hyperbranched resin;
(2) adding the alicyclic epoxy resin and the hydroxyl-terminated hyperbranched resin into a clean and dry stirring tank A with a heating device, heating to 105 ℃ (namely heating the material in the stirring tank A to 105 ℃), and stirring for 15 minutes at a stirring speed of 400 revolutions per minute;
(3) adding a phthalic anhydride curing agent, an alcohol ring-opening agent, a phosphorus-containing accelerator, a hindered phenol antioxidant, an auxiliary antioxidant, a silane coupling agent and a release agent into a clean and dry stirring tank B, and stirring at the stirring speed of 300 revolutions per minute for 20 minutes (stirring at normal temperature) to obtain a first mixed solution;
(4) introducing the first mixed solution in the stirring tank B into the stirring tank A through a conduit, and stirring at the temperature of 105 ℃ (namely heating the material in the stirring tank A to keep the temperature at 105 ℃), wherein the stirring speed is 400 r/min, and the stirring time is 12 min, so as to obtain a second mixed solution;
(5) and adding the second mixed solution into a double-screw extruder through a feed hopper for extrusion, cooling to 25 ℃ to obtain a flaky high-temperature yellowing resistant transparent epoxy molding compound (the material extruded by the extruder can be cooled by adopting methods such as tape casting, calendering and the like to form a flaky material), crushing the flaky high-temperature yellowing resistant transparent epoxy molding compound into a granular material, grinding the granular material into a powder material, and demagnetizing the powder material to obtain the powdery high-temperature yellowing resistant transparent epoxy molding compound.
The obtained powdery transparent epoxy molding compound with high temperature yellowing resistance can be pressed into a cake shape for storage, transportation and use.
The structural formula of the hydroxyl-terminated hyperbranched resin is as follows:
example 4
In this embodiment, the preparation method of the transparent epoxy molding compound with high temperature yellowing resistance comprises the following steps:
(1) the following raw materials are prepared by weight: alicyclic epoxy resin 52.35% (wherein poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3:1) 31.41%, 4-vinyl-1-cyclohexene diepoxide 20.94%), phthalic anhydride curing agent 37.4% (wherein 4-methylhexahydrophthalic anhydride 18.7%, 4-methyltetrahydrophthalic anhydride 18.7%), alcohol ring-opener 2% (all glycerin), phosphorus-containing accelerator 0.4% (all triphenylethyl phosphine bromide), hindered phenol antioxidant 1% (all n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), and auxiliary antioxidant 0.05% (all tris [ 2.4-di-tert-butylphenyl ] phosphite), 0.5% of silane coupling agent (gamma-aminopropyl triethoxysilane), 0.3% of release agent (magnesium stearate) and 6% of hydroxyl-terminated hyperbranched resin;
(2) adding the alicyclic epoxy resin and the hydroxyl-terminated hyperbranched resin into a clean and dry stirring tank A with a heating device, heating to 110 ℃ (namely heating the material in the stirring tank A to 110 ℃), and stirring for 15 minutes at a stirring speed of 400 revolutions per minute;
(3) adding a phthalic anhydride curing agent, an alcohol ring-opening agent, a phosphorus-containing accelerator, a hindered phenol antioxidant, an auxiliary antioxidant, a silane coupling agent and a mold release agent into a clean and dry stirring tank B, and stirring at a stirring speed of 300 revolutions per minute for 10 minutes (stirring at normal temperature) to obtain a first mixed solution;
(4) introducing the first mixed solution in the stirring tank B into the stirring tank A through a conduit, and stirring at the temperature of 110 ℃ (namely heating the material in the stirring tank A to keep the temperature at 110 ℃), wherein the stirring speed is 400 r/min, and the stirring time is 10 min, so as to obtain a second mixed solution;
(5) and adding the second mixed solution into a double-screw extruder through a feed hopper for extrusion, cooling to 28 ℃ to obtain a flaky high-temperature yellowing resistant transparent epoxy molding compound (the material extruded by the extruder can be cooled by adopting methods such as tape casting, calendaring and the like to form a flaky material), crushing the flaky high-temperature yellowing resistant transparent epoxy molding compound into granules, grinding the granules into powder, and demagnetizing the powder to obtain the powdery high-temperature yellowing resistant transparent epoxy molding compound.
The obtained powdery transparent epoxy molding compound with high temperature yellowing resistance can be pressed into a cake shape for storage, transportation and use.
The structural formula of the hydroxyl-terminated hyperbranched resin is as follows:
comparative example
The preparation method of the epoxy molding compound of the comparative example included the following steps:
(1) the following raw materials are prepared by weight: 52.22 percent of phenolic epoxy resin, 35.76 percent of phenolic resin, 4 percent of glycerol, 0.2 percent of triphenyl methyl phosphonium bromide, 0.5 percent of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic n-octadecyl ester, 0.02 percent of trinonyl phenyl phosphite ester, 0.5 percent of gamma-aminopropyl triethoxysilane, 0.8 percent of zinc stearate and 6 percent of liquid carboxyl-terminated butadiene-acrylonitrile rubber;
(2) adding novolac epoxy resin and liquid carboxyl-terminated butadiene-acrylonitrile rubber into a clean and dry stirring tank A with a heating device, heating to 100 ℃ (namely heating the material in the stirring tank A to 100 ℃), and stirring for 10 minutes at a stirring speed of 500 revolutions per minute;
(3) adding phenolic resin, glycerol, triphenyl methyl phosphonium bromide, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, trinonyl phenyl phosphite, gamma-aminopropyl triethoxysilane and zinc stearate into a clean and dry B stirring tank, and stirring at the stirring speed of 500 revolutions per minute for 10 minutes (stirring at normal temperature) to obtain a first mixed solution;
(4) introducing the first mixed solution in the stirring tank B into the stirring tank A through a conduit, and stirring at the temperature of 100 ℃ (namely heating the material in the stirring tank A to keep the temperature at 100 ℃), wherein the stirring speed is 500 revolutions per minute, and the stirring time is 10 minutes to obtain a second mixed solution;
(5) and adding the second mixed solution into a double-screw extruder through a feed hopper for extrusion, cooling to 20 ℃ to obtain a sheet-shaped epoxy molding compound (the material extruded by the extruder can be cooled by adopting methods such as tape casting, calendaring and the like to form a sheet-shaped material), crushing the sheet-shaped epoxy molding compound into granules, grinding the granules into powder, and demagnetizing the powder to obtain the powdery epoxy molding compound.
The transparent epoxy molding materials of examples 1 to 4 and the epoxy molding material of comparative example were subjected to the performance test, and the test methods and test results were as follows:
1. glass transition temperature test
The data were collected according to ISO 11359-2-1999 Standard, using a differential scanning calorimeter model Q20 from TA, USA.
2. Light transmittance test
Data were collected using a model U3900H ultraviolet-visible spectrophotometer, HITACHI, Japan.
3. Flexural Strength and flexural modulus test
The method is carried out according to the GB/T9341 standard, and a TY-8000 type servo control system universal tester of Jiangsu Tianyuan testing equipment Limited company is adopted to collect data.
4. Shear strength test
The data acquisition was carried out according to the SEMI G69-0996 standard using a TY-8000 type servo control system universal tester from Jiangsu Tianyuan test Equipment Co.
The properties of the transparent epoxy molding materials of examples 1,2, 3 and 4 and the epoxy molding materials of comparative examples are shown in Table 1.
TABLE 1
The test result shows that: the transparent epoxy molding compound of the embodiments 1-4 of the invention has high light transmittance, and particularly, after long-time high temperature, the transparent epoxy molding compound of the embodiments 1-4 of the invention can still maintain high light transmittance; the transparent epoxy molding compounds of examples 1 to 4 of the present invention have excellent high temperature yellowing resistance, and do not have yellowing phenomenon after a long time of high temperature. The epoxy molding compound of the comparative example has lower light transmittance, and the transmittance is obviously reduced and the severe yellowing phenomenon occurs after the epoxy molding compound is subjected to high temperature for the same time.
Claims (10)
1. The transparent epoxy molding compound with high temperature yellowing resistance is characterized by being prepared from the following raw materials in parts by weight: 31-60% of alicyclic epoxy resin, 30-50% of phthalic anhydride curing agent, 2-5% of alcohol ring-opening agent, 0.1-1% of phosphorus-containing accelerator, 0.1-1% of hindered phenol antioxidant, 0.01-0.05% of auxiliary antioxidant, 0.1-1% of silane coupling agent, 0.1-1% of mold release agent and 2-10% of hydroxyl-terminated hyperbranched resin;
the preparation method of the high-temperature yellowing resistant transparent epoxy molding compound comprises the following steps:
(1) the following raw materials are prepared by weight: 31-60% of alicyclic epoxy resin, 30-50% of phthalic anhydride curing agent, 2-5% of alcohol ring-opening agent, 0.1-1% of phosphorus-containing accelerator, 0.1-1% of hindered phenol antioxidant, 0.01-0.05% of auxiliary antioxidant, 0.1-1% of silane coupling agent, 0.1-1% of mold release agent and 2-10% of hydroxyl-terminated hyperbranched resin;
(2) adding the alicyclic epoxy resin and the hydroxyl-terminated hyperbranched resin into a clean and dry stirring tank A with a heating device, heating to 110 ℃ at the temperature of 100-;
(3) adding a phthalic anhydride curing agent, an alcohol ring-opening agent, a phosphorus-containing accelerator, a hindered phenol antioxidant, an auxiliary antioxidant, a silane coupling agent and a release agent into a clean and dry stirring tank B, and stirring at a stirring speed of 300-;
(4) introducing the first mixed solution in the stirring tank B into the stirring tank A through a conduit, and stirring at the temperature of 100-110 ℃, wherein the stirring speed is 300-500 r/min, and the stirring time is 5-15 min, so as to obtain a second mixed solution;
(5) and adding the second mixed solution into an extruder through a feed hopper for extrusion, cooling to 20-30 ℃ to obtain the flaky high-temperature yellowing resistant transparent epoxy molding compound, crushing the flaky high-temperature yellowing resistant transparent epoxy molding compound into particles, grinding the particles into powder, and demagnetizing the powder to obtain the powdery high-temperature yellowing resistant transparent epoxy molding compound.
2. The transparent epoxy molding compound with high yellowing resistance as claimed in claim 1, wherein: the alicyclic epoxy resin is one or a mixture of a plurality of poly [ (2-oxiranyl) -1, 2-cyclohexanediol ] 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether (3:1), cyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester and 4-vinyl-1-cyclohexene diepoxide.
3. The transparent epoxy molding compound with high yellowing resistance as claimed in claim 1, wherein: the phthalic anhydride curing agent is one or a mixture of 4-methyl hexahydrophthalic anhydride and 4-methyl tetrahydrophthalic anhydride.
4. The transparent epoxy molding compound with high yellowing resistance as claimed in claim 1, wherein: the alcohol ring-opening agent is one or a mixture of two of ethylene glycol, glycerol and pentaerythritol.
5. The transparent epoxy molding compound with high yellowing resistance as claimed in claim 1, wherein: the phosphorus-containing promoter is one or a mixture of triphenyl methyl phosphonium bromide and triphenyl ethyl phosphonium bromide.
6. The transparent epoxy molding compound with high yellowing resistance as claimed in claim 1, wherein: the hindered phenol antioxidant is one or a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
7. The transparent epoxy molding compound with high yellowing resistance as claimed in claim 1, wherein: the auxiliary antioxidant is one or a mixture of trinonyl phenyl phosphite and tris [2, 4-di-tert-butylphenyl ] phosphite.
8. The transparent epoxy molding compound with high yellowing resistance as claimed in claim 1, wherein: the silane coupling agent is one or a mixture of gamma-glycidoxypropyltrimethoxysilane and gamma-aminopropyltriethoxysilane; the release agent is one or a mixture of zinc stearate and magnesium stearate.
9. The transparent epoxy molding compound with high yellowing resistance as claimed in claim 1, wherein: the structural formula of the hydroxyl-terminated hyperbranched resin is one of the following structural formulas (1) to (3):
10. the method for preparing the high temperature yellowing resistant transparent epoxy molding compound of claim 1, comprising the following steps:
(1) the following raw materials are prepared by weight: 31-60% of alicyclic epoxy resin, 30-50% of phthalic anhydride curing agent, 2-5% of alcohol ring-opening agent, 0.1-1% of phosphorus-containing accelerator, 0.1-1% of hindered phenol antioxidant, 0.01-0.05% of auxiliary antioxidant, 0.1-1% of silane coupling agent, 0.1-1% of mold release agent and 2-10% of hydroxyl-terminated hyperbranched resin;
(2) adding the alicyclic epoxy resin and the hydroxyl-terminated hyperbranched resin into a clean and dry stirring tank A with a heating device, heating to 110 ℃ at the temperature of 100-;
(3) adding a phthalic anhydride curing agent, an alcohol ring-opening agent, a phosphorus-containing accelerator, a hindered phenol antioxidant, an auxiliary antioxidant, a silane coupling agent and a release agent into a clean and dry stirring tank B, and stirring at a stirring speed of 300-;
(4) introducing the first mixed solution in the stirring tank B into the stirring tank A through a conduit, and stirring at the temperature of 100-110 ℃, wherein the stirring speed is 300-500 r/min, and the stirring time is 5-15 min, so as to obtain a second mixed solution;
(5) and adding the second mixed solution into an extruder through a feed hopper for extrusion, cooling to 20-30 ℃ to obtain the flaky high-temperature yellowing resistant transparent epoxy molding compound, crushing the flaky high-temperature yellowing resistant transparent epoxy molding compound into particles, grinding the particles into powder, and demagnetizing the powder to obtain the powdery high-temperature yellowing resistant transparent epoxy molding compound.
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| CN111117165A (en) * | 2020-01-21 | 2020-05-08 | 汕头市骏码凯撒有限公司 | Halogen-free flame-retardant transparent epoxy molding compound and preparation method thereof |
| CN116769278A (en) * | 2023-05-30 | 2023-09-19 | 江苏恒隆通新材料科技有限公司 | Medium-temperature cured flexible epoxy laminated resin |
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