CN115651583A - Packaging adhesive, preparation method thereof and LED element - Google Patents
Packaging adhesive, preparation method thereof and LED element Download PDFInfo
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- CN115651583A CN115651583A CN202211688328.8A CN202211688328A CN115651583A CN 115651583 A CN115651583 A CN 115651583A CN 202211688328 A CN202211688328 A CN 202211688328A CN 115651583 A CN115651583 A CN 115651583A
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a packaging adhesive, a preparation method thereof and an LED element, belonging to the technical field of epoxy resin packaging adhesives; the raw materials of the packaging adhesive comprise epoxy resin, an anhydride curing agent, a curing accelerator, a modifier and an antioxidant; the modifier is trihydroxyethyl isocyanurate or a mixture of the trihydroxyethyl isocyanurate and a polyhydroxy compound; the invention provides a packaging adhesive which has excellent light transmittance and heat resistance; the packaging glue can be used for packaging a molded optical semiconductor device with higher power and lower wavelength, and an optical semiconductor element packaged by the packaging glue has excellent heat-resistant and light-transmitting properties; the glass transition temperature of the packaging adhesive can be improved by adopting the trihydroxyethyl isocyanurate or the mixture of the trihydroxyethyl isocyanurate and the polyhydroxy compound as the modifier.
Description
Technical Field
The invention belongs to the technical field of epoxy resin packaging adhesives, and particularly relates to a packaging adhesive, a preparation method thereof and an LED element.
Background
The mold-sealing resin composition is used for sealing optical semiconductor elements such as Light Emitting Diodes (LEDs) and the like, and transparency is required for the cured product thereof.
Japanese patent JP3442045B2 discloses an epoxy resin composition which is obtained by using an epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin and reacting it with an acid anhydride curing agent and is widely used for various purposes. However, when the epoxy resin composition is used as an encapsulating resin, the material is easily discolored by heat due to the presence of a phenyl structure in the epoxy resin, so that the light transmittance of the material is remarkably reduced.
The US patent US 69889412B 2 discloses an epoxy resin composition, and the use of alicyclic epoxy resin and hybrid epoxy resin can improve the discoloration of the material under heat to some extent. However, when the epoxy resin is used for encapsulating optical semiconductor elements, alkane polyol or polyhydroxy compound is usually added as a modifier to enable the reaction to be carried out smoothly, so as to meet the encapsulation requirement. The use of the alkane polyol or the polyhydroxy compound can obviously lower the glass transition temperature of the B-stage epoxy resin composition, and has a certain reduction effect on the light transmittance of the material.
Disclosure of Invention
The invention provides the packaging adhesive, the preparation method thereof and the LED element aiming at the situations, wherein the packaging adhesive has the characteristics of small influence of glass transition temperature reduction and excellent heat-resistant light-transmitting property.
In order to solve the technical problems, the invention provides an encapsulating adhesive in a first aspect, wherein the raw materials for preparing the encapsulating adhesive comprise epoxy resin, an esterification reactant and a curing accelerator; the esterification reactant is obtained by reacting an anhydride curing agent and a modifier;
the modifier contains trihydroxyethyl isocyanurate. The structure of the modifier, namely the trihydroxyethyl isocyanurate, is a nitrogen heterocyclic ring system, and the structure can be introduced to improve the reaction crosslinking density during the curing of the epoxy resin, so that the glass transition temperature of the epoxy resin packaging adhesive is improved, and the heat resistance yellowing is improved.
According to some embodiments of the present invention, the acid anhydride curing agent is 134.4 to 218.4 parts by weight, the modifier is 13.44 to 21.84 parts by weight, and the curing accelerator is 0.4 to 3.0 parts by weight, based on 100 parts by weight of the epoxy resin.
According to some embodiments of the invention, the modifier further comprises a polyol, wherein the polyol is 50 to 200 parts by weight based on 100 parts by weight of the triethyolisocyanurate.
According to some embodiments of the invention, the raw materials for preparation further comprise an antioxidant;
preferably, the antioxidant is 0.2 to 2.0 parts by weight based on 100 parts by weight of the epoxy resin.
According to some embodiments of the present invention, the epoxy resin is selected from one or more of glycidyl ester type epoxy resin, aliphatic epoxy resin, glycidyl ether type epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin; further preferably, the glycidyl ester type epoxy resin is selected from triglycidyl isocyanurate. Among them, the glycidyl ester type epoxy resin or aliphatic epoxy resin has excellent transparency and discoloration resistance; the epoxy resin may be solid or liquid at normal temperature, and when the epoxy resin is solid, the epoxy resin having a melting point or a softening point of 130 ℃ or less is preferable, and such a material is easy to process; further, an epoxy resin having an epoxy equivalent of 50 to 800 is preferable, and when the epoxy equivalent exceeds 800, the glass transition temperature of the cured material is remarkably lowered.
According to some embodiments of the invention, the anhydride curing agent is selected from one or more of glutaric anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride. The anhydride curing agent has good color transparency, can be solid or liquid at normal temperature, and when the anhydride curing agent is solid, the anhydride curing agent with melting point or softening point of 130 ℃ or below is preferred, and the material is easy to process; further preferably, the acid anhydride curing agent has an acid anhydride equivalent of 100 to 180.
According to some embodiments of the invention, the cure accelerator is selected from one or more of 1, 8-diazabicyclo [5.4.0] undec-7-ene, N-N-diethylaniline, 2-ethyl-4-methylimidazole, 2-methylimidazole, undecylimidazole, triphenylphosphine chloride, triphenylphosphine bromide, tetraphenylphosphine, benzyltriphenylphosphine bromide, tetrabutylO, O-diethyldithiophosphophosphine.
According to some embodiments of the present invention, the antioxidant is selected from one or more of phenol compounds, ammonia compounds, organic sulfur compounds, phosphorus compounds; preferably, the phenol compound can be selected from one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2, 6-di-tert-butyl-p-cresol and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the ammonia compound is selected from poly { [6- [ (1, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2, 6, -tetramethyl-piperidyl) imino ] -1, 6-hexamethylene [ (2, 6-tetramethyl-4-piperidyl) imino ] }, one or more of butyl octylated diphenylamine; the organic sulfur compound is one or more selected from 2,2' -thiobis (4-methyl-6-tert-butylphenol), 3- (dodecylthio) propionic acid-2, 2-bis [ [3- (dodecylthio) -propionyloxy ] methyl ] -1, 3-propylene glycol ester; the phosphine compound is selected from one or more of phosphite ester and triphenyl phosphite; the antioxidant can be mixed with the packaging adhesive at will.
According to some embodiments of the invention, the polyol is selected from a polyol or a polyester polyol; preferably, the polyalcohol is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol and pentaerythritol; the polyester polyol is selected from one or more of aliphatic polyester polyol, adipic acid polyester polyol, unsaturated aliphatic polyester polyol, caprolactone polyester polyol, aromatic polyester polyol and aromatic polyester polyol.
The second aspect of the present invention provides a method for preparing the above encapsulation adhesive, including: and curing the epoxy resin, the esterification reactant and the curing accelerator to obtain the packaging adhesive.
According to some embodiments of the present invention, the curing is a partial curing, which results in a B-staged epoxy encapsulant; the partial curing means that the curing degree of the epoxy resin sealing adhesive is advanced until the sealing adhesive has a gelation time of 10 seconds to 70 seconds, preferably 20 seconds to 40 seconds, at a temperature of 150 ℃.
According to some embodiments of the invention, the esterification reactant is derived from the reaction of an anhydride curing agent and a modifier; preferably, the reaction temperature is 60 ℃ to 180 ℃, such as 60 ℃, 120 ℃, 180 ℃; the reaction time is 30min to 90min, such as 30min, 60min and 90min.
According to some embodiments of the invention, upon curing, an antioxidant is also added; preferably, the curing temperature is 40 ℃ to 100 ℃, such as 40 ℃, 60 ℃, 80 ℃, 100 ℃, and the curing time is 1h to 18h, such as 1h, 2h, 5h, 9h, 11h, 18h. Curing at lower temperatures helps to accelerate the molding time during the subsequent mold encapsulation step, resulting in superior moldability during the subsequent mold encapsulation step.
According to some embodiments of the present invention, during the mixing, the epoxy resin, the esterification reactant, the antioxidant and the curing accelerator are mixed for 10min to 40min, such as 10min, 20min and 40min, and then the mixture is further mixed for 20min to 60min at an adjusted temperature of 60 ℃ to 100 ℃, such as 60min at an adjusted temperature, 20min at an adjusted temperature of 80 ℃ and 30min at an adjusted temperature of 100 ℃.
The third aspect of the present invention provides the above-mentioned sealing adhesive, wherein the gelation time at a temperature of 150 ℃ is 10 seconds to 70 seconds, preferably 20 seconds to 40 seconds.
A fourth aspect of the present invention provides an LED element comprising:
an LED chip and an encapsulation layer covering the LED chip; the packaging layer is composed of the packaging adhesive.
In the present invention, the type of the LED chip is not particularly limited, and a type commonly used in the art may be used.
In the present invention, the formation process of the encapsulation layer is not particularly limited, and a process known in the art may be used. For example, the forming process may include the steps of: applying the packaging adhesive of the invention on the LED chip, and then curing the packaging adhesive of the invention to form the packaging layer. The manner of application is not particularly limited and processes well known in the art may be employed. The curing time and curing temperature of the curing are not particularly limited.
In the present invention, the thickness of the encapsulation layer is not particularly limited, and a thickness known in the art may be used.
Has the advantages that:
the invention provides a packaging adhesive which has excellent light transmittance and heat resistance;
the packaging adhesive prepared by the invention can be used for packaging the die pressing optical semiconductor device with higher power and lower wavelength, and the optical semiconductor element packaged by the packaging adhesive has excellent heat resistance and light transmittance;
the packaging adhesive provided by the invention adopts the trihydroxyethyl isocyanurate or the mixture of the trihydroxyethyl isocyanurate and the polyhydroxy compound as the modifier, so that the glass transition temperature of the packaging adhesive can be increased, the heat-aging-resistant light-transmitting property of the packaging adhesive can be improved, and the thermal decomposition temperature can be increased to a certain extent.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
The equivalent weight of acid anhydride in the present invention means the number of grams of acid anhydride containing one equivalent of acid anhydride group in (g/equivalent), i.e., the value of the molecular weight of the acid anhydride divided by the number of epoxy groups contained per molecule;
the epoxy equivalent in the present invention means the number of grams of epoxy resin containing one equivalent of epoxy group, and the unit is (gram/equivalent), that is, the average molecular weight of the epoxy resin is divided by the number of epoxy groups contained in each molecule;
the curing is carried out in a B-stage reactor capable of realizing partial curing of the packaging adhesive, and the common commercially available B-stage reactor can be used;
the gelation time of the partially cured packaging adhesive in the invention is tested according to SJ/T11197-2013 epoxy plastic package material; during testing, the electric heating plate is heated to 150 +/-1 ℃, 0.3-0.5 g of sample is taken and placed on the electric heating plate, the flattening area of the sample is 5cm, when the melting is started, one end of the needle-shaped stirring rod or a flat shovel is used for stirring, the partially cured packaging adhesive gradually changes from a fluid state to a gel state (the sample cannot be pulled into wires) as an end point, the required time is read, the same operation is repeated twice, and the average value of the operation is taken.
Example 1
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting for 90min at the temperature of 60 ℃ to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The gelation time of the above partially cured encapsulant was 20 seconds at a temperature of 150 deg.C.
Example 2
The embodiment provides a packaging adhesive, which is prepared by the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting for 60min at the temperature of 120 ℃ to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The gelation time of the above partially cured encapsulant was 40 seconds at a temperature of 150 deg.C.
Example 3
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting at 180 ℃ for 30min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The partially cured encapsulant had a gel time of 35 seconds at a temperature of 150 c.
Example 4
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting for 30min at the temperature of 180 ℃ to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 10min, adjusting the temperature of the mixture to 100 ℃, continuously mixing for 30min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The partially cured encapsulant had a gelation time of 26 seconds at a temperature of 150 c.
Example 5
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting at 180 ℃ for 30min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 20min, adjusting the temperature of the mixture to 80 ℃, continuously mixing for 20min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The partially cured encapsulant had a gelation time of 32 seconds at a temperature of 150 c.
Example 6
The embodiment provides a packaging adhesive, which is prepared by the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting at 180 ℃ for 30min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 20min, adjusting the temperature of the mixture to 80 ℃, continuously mixing for 20min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 40 ℃ and the curing time is 18h.
The gelation time of the above partially cured encapsulant was 17 seconds at a temperature of 150 c.
Example 7
The embodiment provides a packaging adhesive, which is prepared by the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting for 30min at the temperature of 180 ℃ to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent 100), 1g of tetrabutyl O, O-diethyl phosphorodithioate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 20min, adjusting the temperature of the mixture to 80 ℃, continuously mixing for 20min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 60 ℃ and the curing time is 11h.
The partially cured encapsulant had a gelation time of 57 seconds at a temperature of 150 c.
Example 8
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting at 180 ℃ for 30min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 20min, adjusting the temperature of the mixture to 80 ℃, continuously mixing for 20min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 100 ℃, and the curing time is 1h.
The partially cured encapsulant had a gelation time of 46 seconds at a temperature of 150 c.
Example 9
The embodiment provides a packaging adhesive, which is prepared by the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting for 30min at the temperature of 180 ℃ to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 20min, adjusting the temperature of the mixture to 80 ℃, continuously mixing for 20min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 100 ℃, and the curing time is 2h.
The gelation time of the above partially cured encapsulant was 11 seconds at a temperature of 150 ℃.
Example 10
The embodiment provides a packaging adhesive, which is prepared by the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting at 180 ℃ for 30min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 20min, adjusting the temperature of the mixture to 80 ℃, continuously mixing for 20min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 60 ℃ and the curing time is 9h.
The partially cured encapsulant had a gelation time of 68 seconds at a temperature of 150 c.
To further illustrate the advancement of the present invention, the partially cured encapsulant prepared in examples 1-10 above was measured and evaluated for glass transition temperature, light transmission and heat resistance, and thermal decomposition temperature as follows;
glass transition temperature:
the partially cured encapsulant prepared in examples 1-10 was formed into a cured test block of 70mm by 5mm (curing conditions: first cured at 170 ℃ for 4min and then at 150 ℃ for 4 h); respectively heating the test blocks from 25 ℃ to 260 ℃ at a heating rate of 5 ℃/min by using a thermal analyzer (TA instruments-waters LLC, Q400), and measuring the glass transition temperature of the test blocks in the process;
(II) light transmission and heat resistance:
the partially cured encapsulant prepared in examples 1-10 was prepared into a cured product test block with a block size of 1mm in thickness and a bottom area of 20mm × 20mm (curing conditions: first curing at 170 ℃ for 4min and then at 150 ℃ for 4 h); respectively testing the light transmittance change of the test blocks at different times in a normal pressure environment at the temperature of 150 ℃; a light transmittance test with a wavelength of 450nm is carried out by using a color measuring agent at a temperature of 25 ℃; the test equipment was a color measuring instrument (KONICA MINOLTA, CM-3600A);
(III) thermal decomposition temperature:
the partially cured encapsulant prepared in examples 1-10 was separately prepared into a cured product test piece weighing 15mg (curing conditions: first cured at 170 ℃ for 4min, then cured at 150 ℃ for 4 h); respectively heating the test object from 25 ℃ to 800 ℃ at a heating rate of 20 ℃/min by using a thermal weight loss analyzer (Mettler Toledo, TGA 2), and measuring the thermal decomposition temperature of the test object in the process;
the evaluation results are shown in Table 1.
TABLE 1 Performance parameters of partially cured encapsulant prepared in examples 1-10
Example 11
The embodiment provides a packaging adhesive, which is prepared by the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of trihydroxyethyl isocyanurate, and reacting for 60min at the temperature of 120 ℃ to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The gelation time of the above partially cured encapsulant was 40 seconds at a temperature of 150 deg.C.
Example 12
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168), 12.6g of trihydroxyethyl isocyanurate and 4.2g of glycerol, and reacting at 120 ℃ for 60min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent 100), 1g of tetrabutyl O, O-diethyl phosphorodithioate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The gelation time of the above partially cured encapsulant was 40 seconds at a temperature of 150 deg.C.
Example 13
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168), 8.4g of trihydroxyethyl isocyanurate and 8.4g of glycerol, and reacting at 120 ℃ for 60min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The partially cured encapsulant had a gelation time of 40 seconds at a temperature of 150 c.
Example 14
The embodiment provides a packaging adhesive, which is prepared by the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168), 4.2g of trihydroxyethyl isocyanurate and 12.6g of glycerol, and reacting at 120 ℃ for 60min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent 100), 1g of tetrabutyl O, O-diethyl phosphorodithioate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The gelation time of the above partially cured encapsulant was 40 seconds at a temperature of 150 deg.C.
Example 15
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168), 8.4g of trihydroxyethyl isocyanurate and 8.4g of neopentyl glycol, and reacting at 120 ℃ for 60min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The partially cured encapsulant had a gelation time of 40 seconds at a temperature of 150 c.
Example 16
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 134.4g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 13.44g of trihydroxyethyl isocyanurate, and reacting for 60min at the temperature of 120 ℃ to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The gelation time of the above partially cured encapsulant was 40 seconds at a temperature of 150 deg.C.
Example 17
The embodiment provides a packaging adhesive, which is prepared by the following steps:
mixing 151.2g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 15.12g of trihydroxyethyl isocyanurate, and reacting at 120 ℃ for 60min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The gelation time of the above partially cured encapsulant was 40 seconds at a temperature of 150 deg.C.
Example 18
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 193.2g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 19.32g of trihydroxyethyl isocyanurate, and reacting for 60min at the temperature of 120 ℃ to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The partially cured encapsulant had a gelation time of 40 seconds at a temperature of 150 c.
Example 19
The embodiment provides a packaging adhesive, and the preparation method comprises the following steps:
mixing 218.4g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 21.84g of trihydroxyethyl isocyanurate, and reacting at 120 ℃ for 60min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent 100), 1g of tetrabutyl O, O-diethyl phosphorodithioate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The gelation time of the above partially cured encapsulant was 40 seconds at a temperature of 150 deg.C.
Comparative example 1
The comparative example further provides an encapsulant prepared as follows
Mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of glycerol, and reacting at 120 ℃ for 60min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The gelation time of the above partially cured encapsulant was 40 seconds at a temperature of 150 deg.C.
Comparative example 2
The comparative example further provides an encapsulant prepared as follows
Mixing 168g of methylhexahydrophthalic anhydride (anhydride equivalent 168) and 16.8g of neopentyl glycol, and reacting at 120 ℃ for 60min to obtain an esterification reactant;
adding 100g of triglycidyl isocyanurate (epoxy equivalent of 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into the esterification reactant, mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain the partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The partially cured encapsulant had a gelation time of 40 seconds at a temperature of 150 c.
Comparative example 3
The comparative example further provides an encapsulation adhesive, which is prepared as follows
Adding 99g of triglycidyl isocyanurate (epoxy equivalent 100), 1g of tetrabutyl O, O-diethyldithiophosphate and 1g of 2, 6-di-tert-butyl-p-cresol into 100g of bisphenol A epoxy resin (epoxy equivalent 170), mixing for 40min, adjusting the temperature of the mixture to 60 ℃, continuously mixing for 60min, and curing to obtain a partially cured packaging adhesive, wherein the curing process conditions are as follows: the curing temperature is 80 ℃ and the curing time is 5h.
The partially cured encapsulant had a gelation time of 40 seconds at a temperature of 150 c.
The partially cured encapsulant prepared in examples 11 to 19 and comparative examples 1 to 3 were subjected to performance evaluation by measuring and evaluating the glass transition temperature, light transmittance and heat resistance, and thermal decomposition temperature in examples 1 to 10, respectively; the evaluation results are shown in Table 2 below.
TABLE 2 Performance parameters of the partially cured encapsulant prepared in examples 11-19 and comparative examples 1-3
The performance data in table 2 show that the use of the modifier of the invention, tris (hydroxyethyl isocyanurate), can increase the glass transition temperature of the packaging adhesive, improve the thermal aging resistance and light transmittance of the packaging adhesive, and increase the thermal decomposition temperature to a certain extent; when the packaging adhesive is prepared according to the comparative examples 1 and 2, only polyhydroxy compounds are used as the modifier, the glass transition temperature is lower, and the heat aging resistance and light transmittance are poor; comparative example 3 when the encapsulation adhesive was prepared, the glass transition temperature and the thermal aging resistance and light transmittance of the prepared encapsulation adhesive were both significantly reduced by using the bisphenol a type epoxy resin without adding the modifier.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. The packaging adhesive is characterized in that the preparation raw materials of the packaging adhesive comprise epoxy resin, an esterification reactant and a curing accelerator; the esterification reactant is obtained by reacting an anhydride curing agent and a modifier;
the modifier contains trihydroxyethyl isocyanurate.
2. The packaging adhesive according to claim 1, wherein the acid anhydride curing agent is 134.4 to 218.4 parts by weight, the modifier is 13.44 to 21.84 parts by weight, and the curing accelerator is 0.4 to 3.0 parts by weight, based on 100 parts by weight of the epoxy resin;
preferably, the modifier also comprises a polyhydroxy compound, and the polyhydroxy compound is 50-200 parts by weight based on 100 parts by weight of the trihydroxyethyl isocyanurate.
3. The packaging adhesive of claim 2, wherein the raw materials further comprise an antioxidant;
preferably, the antioxidant is 0.2 to 2.0 parts by weight based on 100 parts by weight of the epoxy resin.
4. The packaging adhesive according to any one of claims 1 to 3, wherein the epoxy resin has an epoxy equivalent of 50 to 800; preferably, the epoxy resin is selected from one or more of glycidyl ester type epoxy resin, aliphatic epoxy resin, glycidyl ether type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin and naphthalene type epoxy resin; further preferably, the glycidyl ester type epoxy resin is selected from triglycidyl isocyanurate;
and/or the anhydride equivalent of the anhydride curing agent is 100 to 180; preferably, the anhydride curing agent is selected from one or more of glutaric anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride;
and/or the curing accelerator is one or more selected from 1, 8-diazabicyclo [5.4.0] undec-7-ene, N-N-diethylaniline, 2-ethyl-4-methylimidazole, 2-methylimidazole, undecylimidazole, triphenylphosphine chloride, triphenylphosphine bromide, tetraphenylphosphine, benzyltriphenylphosphine bromide, tetrabutyl O, O-diethylphosphorodithioate.
5. The packaging adhesive according to any one of claims 1 to 3, wherein the antioxidant is selected from one or more of phenol compounds, ammonia compounds, organic sulfur compounds and phosphorus compounds; preferably, the phenolic compound is selected from one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2, 6-di-tert-butyl-p-cresol and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the ammonia compound is selected from poly { [6- [ (1, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2, 6, -tetramethyl-piperidyl) imino ] -1, 6-hexamethylene [ (2, 6-tetramethyl-4-piperidyl) imino ] }, one or more of butyl octylated diphenylamine; the organic sulfur compound is one or more selected from 2,2' -thiobis (4-methyl-6-tert-butylphenol), 3- (dodecylthio) propionic acid-2, 2-bis [ [3- (dodecylthio) -propionyloxy ] methyl ] -1, 3-propylene glycol ester; the phosphine compound is selected from one or more of phosphite ester and triphenyl phosphite.
6. The encapsulating adhesive according to any of claims 1 to 3, wherein the polyol is selected from a polyol or a polyester polyol; preferably, the polyalcohol is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol and pentaerythritol; the polyester polyol is selected from one or more of aliphatic polyester polyol, adipic acid polyester polyol, unsaturated aliphatic polyester polyol, caprolactone polyester polyol, aromatic polyester polyol and aromatic polyester polyol.
7. A method for preparing the packaging adhesive according to any one of claims 1 to 6,
the method comprises the following steps: and mixing and curing the epoxy resin, the esterification reactant and the curing accelerator to obtain the packaging adhesive.
8. The method according to claim 7, wherein an antioxidant is further added during the mixing; preferably, during the mixing, the mixture is mixed for 10min to 40min, and then the temperature is adjusted to 60 ℃ to 100 ℃ to continue mixing for 20min to 60min;
and/or the curing temperature is 40-100 ℃, and the curing time is 1-18 h;
and/or the esterification reactant is obtained by reacting an anhydride curing agent and a modifying agent; preferably, the reaction temperature is 60-180 ℃, and the reaction time is 30-90 min.
9. An encapsulation adhesive according to any one of claims 1 to 6 or an encapsulation adhesive prepared by the preparation method according to claim 7 or 8, wherein the gelation time at a temperature of 150 ℃ is 10 seconds to 70 seconds, preferably 20 seconds to 40 seconds.
10. An LED element, characterized in that the LED element comprises:
an LED chip and an encapsulation layer covering the LED chip;
wherein the packaging layer is composed of the packaging adhesive of any one of claims 1 to 6 or 9 or the packaging adhesive prepared by the preparation method of claim 7 or 8.
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| CN202211688328.8A CN115651583A (en) | 2022-12-28 | 2022-12-28 | Packaging adhesive, preparation method thereof and LED element |
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| CN202211688328.8A CN115651583A (en) | 2022-12-28 | 2022-12-28 | Packaging adhesive, preparation method thereof and LED element |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102365309A (en) * | 2009-04-03 | 2012-02-29 | 库克复合材料和聚合物公司 | Thermosetting compositions containing isocyanurate rings |
| CN102532483A (en) * | 2010-11-30 | 2012-07-04 | 东洋油墨Sc控股株式会社 | Thermosetting resin compound containing carboxyl modified polyurethane resin |
| US20130203898A1 (en) * | 2012-02-03 | 2013-08-08 | Anna Mueller-Cristadoro | Hyperbranched polymers for modifying the toughness of cured epoxy resin systems |
| CN104991419A (en) * | 2015-07-02 | 2015-10-21 | 惠州市容大油墨有限公司 | Photocuring thermocuring resin composition, application and circuit board using same |
-
2022
- 2022-12-28 CN CN202211688328.8A patent/CN115651583A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102365309A (en) * | 2009-04-03 | 2012-02-29 | 库克复合材料和聚合物公司 | Thermosetting compositions containing isocyanurate rings |
| CN102532483A (en) * | 2010-11-30 | 2012-07-04 | 东洋油墨Sc控股株式会社 | Thermosetting resin compound containing carboxyl modified polyurethane resin |
| US20130203898A1 (en) * | 2012-02-03 | 2013-08-08 | Anna Mueller-Cristadoro | Hyperbranched polymers for modifying the toughness of cured epoxy resin systems |
| CN104991419A (en) * | 2015-07-02 | 2015-10-21 | 惠州市容大油墨有限公司 | Photocuring thermocuring resin composition, application and circuit board using same |
Non-Patent Citations (3)
| Title |
|---|
| "常用树脂对IC封装用环氧塑封料性能影响" * |
| 曾亮等: "大功率IGBT用耐高温环氧胶的研制" * |
| 益小苏，李岩编著, 中国建材工业出版社 * |
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