CN111534260A - Epoxy resin packaging adhesive and preparation method and application thereof - Google Patents
Epoxy resin packaging adhesive and preparation method and application thereof Download PDFInfo
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- CN111534260A CN111534260A CN202010334972.XA CN202010334972A CN111534260A CN 111534260 A CN111534260 A CN 111534260A CN 202010334972 A CN202010334972 A CN 202010334972A CN 111534260 A CN111534260 A CN 111534260A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses an epoxy resin packaging adhesive, which comprises a component A and a component B; the component A comprises the following components: epoxy resin, antioxidant, accelerator A, filler and modified phyllosilicate; the component B comprises the following components: acid anhydride, accelerator B and coupling agent; preferably, the mass ratio of the component A to the component B is 1: (0.2-1.2). The epoxy resin packaging adhesive has the excellent characteristics of high temperature and high humidity resistance, maintains good mechanical properties, and can be used as an LED packaging adhesive.
Description
Technical Field
The invention relates to an epoxy resin packaging adhesive, a preparation method thereof and a packaging method using the epoxy resin packaging adhesive, belonging to the field of LED packaging materials.
Background
As a novel light source, the LED has the advantages of low energy consumption and low pollution compared with the traditional mode, and has a better development prospect.
At present, an LED is mainly packaged by epoxy resin, and a resin shell after the LED is packaged mainly has the following functions: the chip is protected from external erosion. The epoxy resin has the advantages of good comprehensive mechanical property, high bonding strength, wide bonding surface, low shrinkage rate, good stability, excellent electrical insulation property and good processability, and can be widely applied to the field of LED packaging materials. However, since the viscosity of epoxy resin is generally high and the crosslinking density is high, the epoxy resin has the disadvantages of large internal stress, poor fatigue resistance, poor heat resistance, poor moisture resistance and the like, and the application of the epoxy resin in the aspect of structural materials is greatly restricted. Therefore, the design and development of the epoxy resin packaging material are enhanced, the humidity resistance and the heat resistance of the epoxy resin are improved, and the epoxy resin packaging material has certain economic and social significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides an epoxy resin packaging adhesive and a preparation method thereof.
According to one aspect of the invention, an epoxy resin packaging adhesive is provided, which comprises an A component and a B component; the component A comprises the following components: epoxy resin, antioxidant, accelerator A, filler and modified phyllosilicate; the component B comprises the following components: anhydride, accelerator B and coupling agent.
According to a preferred embodiment of the invention, the mass ratio of the a component and the B component is 1:
(0.2-1.2), for example, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.1, and any value therebetween, preferably 1: (0.4-1.0), more preferably 1: (0.5-0.7).
The inventor finds in research that the water-resisting and moisture-resisting performance can be achieved by adding a certain amount of layered silicate into the epoxy resin packaging adhesive, and finds in specific experiments that: the phyllosilicate filler with a sheet microstructure has lower water absorption rate in a water absorption rate test compared with a common filler.
According to a preferred embodiment of the present invention, the phyllosilicate comprises one or more of pyrophyllite, zeolite powder, attapulgite, talc, mica, kaolin, bentonite, serpentine powder, chlorite powder and montmorillonite.
According to a preferred embodiment of the invention, the phyllosilicate comprises one or more of bentonite, laponite, hydrobentonite, stevensonite, beidellite, sodiumdiolite, hectorite, copper montmorillonite and chromium montmorillonite.
According to a preferred embodiment of the present invention, the modified layered silicate is prepared by a method comprising the steps of:
1) intercalation treatment is carried out on the layered silicate by using an organic intercalation agent to obtain an intercalation product;
2) and modifying the intercalation product by using epoxy resin to obtain the modified phyllosilicate.
According to a preferred embodiment of the present invention, the step 1) comprises: carrying out ultrasonic treatment on the solution containing the layered silicate and the organic intercalation agent, and then drying an ultrasonic product to obtain an intercalation product.
According to a preferred embodiment of the invention, the mass ratio of the phyllosilicate to the organic intercalant is 100: (0.01-5), for example, 100:0.5, 100:1, 100:1.5, 100:2, 100:2.5, 100:3, 100:3.5, 100:4 and 100:4.5 and any value in between.
According to a preferred embodiment of the present invention, the solution containing the layered silicate and the organic intercalating agent can be prepared according to experience of a person skilled in the art, for example, by mixing the layered silicate, the organic intercalating agent and water and stirring them uniformly.
According to a preferred embodiment of the present invention, the amount of water used in preparing the solution may be controlled according to the specific situation, for example, the mass ratio of the layered silicate to the organic intercalant to water is 100: (0.01-5): (150-250).
According to a preferred embodiment of the present invention, the water is ultrapure water.
According to the preferred embodiment of the invention, the power of the ultrasonic treatment in the step 1) is 10-1000W, the ultrasonic frequency is 10-100KHz, the ultrasonic time is 5-60min, and the temperature is 30-150 ℃.
According to a preferred embodiment of the invention, the temperature of the drying treatment is 70 to 100 ℃, preferably 80 ℃.
In some specific embodiments, the step 1) may be performed as follows: the layered silicate, the organic intercalation agent and water are placed in a beaker, the mixture is uniformly stirred, then the solution is subjected to ultrasonic treatment, and then an ultrasonic product is dried to obtain the intercalation product.
According to a preferred embodiment of the present invention, the organic intercalating agent comprises an alkyl quaternary ammonium salt, preferably a C12-18 alkyl quaternary ammonium salt, more preferably one or more of dodecyl trimethyl ammonium halide, tetradecyl trimethyl ammonium halide, hexadecyl trimethyl ammonium halide, octadecyl bis-hydroxyethyl methyl ammonium halide, dodecyl dimethyl benzyl ammonium halide, tetradecyl dimethyl benzyl ammonium halide, hexadecyl dimethyl benzyl ammonium halide and octadecyl dimethyl benzyl ammonium halide.
In some specific embodiments, the organic intercalant comprises one or more of dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, octadecyldihydroxyethyl methylammonium chloride, octadecyldihydroxyethyl methylammonium bromide, dodecyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium bromide, tetradecyldimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium bromide, hexadecyldimethylbenzylammonium chloride, hexadecyldimethylbenzylammonium bromide, octadecyldimethylbenzylammonium chloride, and octadecyldimethylbenzylammonium bromide.
The alkyl quaternary ammonium salt can enter between the layered silicate sheets through ion exchange reaction, the interlayer spacing can be enlarged by longer alkyl molecular chains, so that resin molecules (such as epoxy resin) can be inserted between the layered silicate sheets, in addition, active H carried by the quaternary ammonium salt can perform chemical reaction with epoxy groups of the epoxy resin, and a chemical bond is formed and is firmly combined with epoxy.
At the moment, the long alkyl chains on the organic ions cover the surface of the sheet layer, so that the surface hydrophilicity is reduced, the lipophilicity is greatly improved, and the binding force between the modified phyllosilicate and the polymer is enhanced.
According to a preferred embodiment of the present invention, the step 2) comprises:
2A) carrying out ultrasonic treatment on a mixture containing an intercalation product, epoxy resin, an accelerant C and a solvent to obtain an ultrasonic product;
2B) removing the solvent in the ultrasonic product obtained in the step 2A) to obtain the modified phyllosilicate.
According to a preferred embodiment of the invention, the ratio by mass of the intercalated product and the epoxy resin is 100:
(10-30), which may be, for example, 100: 15. 100:18, 100:20, 100:23, 100:25, and 100:28, and any value in between.
According to a preferred embodiment of the invention, the ratio by mass of the intercalation product and accelerator C is 100:
(0.01-5), for example, 100:0.5, 100:1, 100:1.5, 100:2, 100:2.5, 100:3, 100:3.5, 100:4 and 100:4.5 and any value in between.
According to a preferred embodiment of the invention, the ratio by mass of the intercalation product and the solvent is 100:
(100-.
According to a preferred embodiment of the present invention, the solvent in step 2A) comprises one or more of isopentane, n-pentane, petroleum ether, hexane, cyclohexane, isooctane, trimethylpentane, cyclopentane, butyryl chloride, heptane, trichloroethylene, carbon tetrachloride, trichlorotrifluoroethane, propyl ether, toluene, xylene, chlorobenzene, o-dichlorobenzene, diethyl ether, benzene, isobutanol, dichloromethane, ethylene dichloride, n-butanol, butyl acetate, propanol, methyl isobutyl ketone, tetrahydrofuran, ethyl acetate, isopropanol, trichloromethane, methyl ethyl ketone, dioxane, pyridine, acetone, nitromethane, acetonitrile, dimethylformamide, methanol, ethylene glycol and dimethylsulfoxide, preferably xylene.
According to the preferred embodiment of the invention, the power of the ultrasonic treatment in the step 2A) is 10-1000W, the ultrasonic frequency is 10-100KHz, the ultrasonic time is 5-60min, and the temperature is 30-150 ℃.
According to a preferred embodiment of the invention, said step 2A) can be carried out as follows: and (3) placing the intercalation product, epoxy resin, an accelerant C and a solvent into a container, sealing, and then carrying out ultrasonic treatment to obtain an ultrasonic product.
According to a preferred embodiment of the present invention, the solvent in the ultrasonic product obtained in step 2A) is removed by distillation under reduced pressure in step 2B) to obtain the modified layered silicate.
According to a preferred embodiment of the invention, the temperature of the reduced pressure distillation is between 40 and 150 ℃, preferably between 70 and 90 ℃.
The existence of the layered silicate can increase the steric hindrance of the reaction of the epoxy group and the anhydride group, thereby causing the increase of the residual active functional groups and the reduction of the crosslinking density, and further influencing the related performance of the packaging adhesive. The intercalation agent reacts with the epoxy resin to enable the layered silicate to have a certain number of epoxy groups, so that the sheet layer can also participate in the resin curing to form a part of a three-dimensional network structure, and the crosslinking density is not greatly influenced.
According to a preferred embodiment of the present invention, the epoxy resin comprises 2, 3-epoxypropyl acrylate, bis (3, 4-epoxycyclohexylmethyl) adipate, 3, 4-epoxycyclohexylmethyl formate-3 ',4' -epoxycyclohexylmethyl ester, 3, 4-epoxy-6-methylcyclohexanecarboxylic acid-3 ',4' -epoxy-6 ' -methylcyclohexanemethyl ester, dicyclopentadiene diepoxy, bis- (2, 3-epoxycyclopentyl) -ether, 3, 4-epoxycyclohexylmethyl-2 ',3' -epoxycyclohexyl ether, bis- (2, 3-epoxycyclohexane), 1, 2-bis- (2, 3-epoxycyclohexyloxy) -ethane, bis- (2, 3-epoxycyclohexyl) ether, 1-bis (2',3' -epoxycyclohexyloxymethyl) -3, 4-epoxycyclohexane, diglycidyl phthalate, 4-dihydroxydiphenylsulfone diglycidyl ether, tetraphenolethane tetraglycidyl ether, resorcinol diglycidyl ether, phloroglucinol glycidyl, p-resorcinol acetal tetraglycidyl ether, p-aminophenol epoxy resin, 4, 4' diaminodiphenylmethane tetraglycidyl amine, 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid epoxy resin, tetrahydrobenzene dimethyl ester epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, linear bisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin and organosilicon modified epoxy resin.
According to a preferred embodiment of the present invention, the bisphenol a type epoxy resin includes one or more of dow DER-330(330 bisphenol a epoxy resin), DER-331(331 bisphenol a epoxy resin), DER-332(332 bisphenol a epoxy resin), DER-144(144 bisphenol a epoxy resin), DER-671(671 bisphenol a epoxy resin).
According to a preferred embodiment of the present invention, the bisphenol S type epoxy resin includes one or more of DER-352(352 bisphenol S epoxy resin), DER-353(353 bisphenol S epoxy resin), DER-354(354 bisphenol S epoxy resin) manufactured by dow chemistry.
According to a preferred embodiment of the present invention, the silicone-modified epoxy resin comprises one or more of grade numbers EPSI-3201, EPSI-3202X, EPSI-6262, EPSI-3266, EPSI-6278, EPSI-3203X, EPSI-3866, EPSI-6862, EPSI-6878, EPSI-6200X and EPSI-6258X, which are manufactured by Complex high-New materials (Shanghai) Ltd.
The organic silicon modified epoxy resin has the physical properties of reinforced materials, and not only can reduce the internal stress of the epoxy resin, but also can increase the toughness, high temperature resistance and other properties of the epoxy resin. The main chain of the organic silicon resin mainly consists of Si-O bonds, the Si-O bonds are long, the flexibility is good, and the bond energy of the organic silicon resin is larger than that of C-C bonds and C-O bonds, so that the organic silicon resin has good heat resistance and weather resistance.
According to a preferred embodiment of the present invention, the antioxidant comprises n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-tert-butyl-4-methylphenol, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis (beta- (3, 5-tert-butyl-4-methylphenyl) propionate), spiroglycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], 2-ethylidenebis (4, 6-di-tert-butylbenzene) fluorophosphite, triphenyl phosphite, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, trioctyl, One or more of tridecyl ester, tridodecyl ester, trihexadecyl ester, diphenylamine, p-phenylenediamine, and dihydroquinoline.
In a particular embodiment of the invention, the accelerators A, B and C may be the same or different.
According to a preferred embodiment of the present invention, the promoter a comprises one or more of acetylacetone metal salts, β -diketone metal complexes, ethyltriphenylphosphonium iodide and triphenylphosphine, preferably comprising one or more of cobalt acetylacetonate hydrate, beryllium acetylacetonate, indium acetylacetonate, gallium acetylacetonate, chromium acetylacetonate, hafnium acetylacetonate, ferrous acetylacetonate, lithium acetylacetonate, strontium acetylacetonate hydrate, manganese acetylacetonate, zinc acetylacetonate, β -diketone europium complexes, β -diketone manganese complexes, β -diketone titanium complexes and β -diketone chromium complexes.
According to a preferred embodiment of the present invention, the accelerator B comprises one or more of N- (2-cyanoethyl) caprolactam, diethylenetriamine, triethylenetetramine, polyethylene polyamine, tetramethylammonium bromide, tetraethylammonium bromide or tetrabutylammonium bromide, N-p-chlorophenyl-N ', N' -dimethylurea, dimethylimidazolium urea, 2-ethyl-4-methylimidazole, boron trifluoride amine complex, complex nanotitanium dioxide, benzyldimethylamine, pyridine, trimethylamine, triethylamine, triethanolamine, N, N-dimethylaniline, triethylamine, triethanolamine, dimethylethanolamine, propylene glycol, glycerol, neopentyl glycol.
According to a preferred embodiment of the present invention, said promoter C comprises one or more of acetylacetone metal salts, β -diketone metal complexes, ethyltriphenylphosphonium iodide and triphenylphosphine, preferably comprising one or more of cobalt acetylacetonate hydrate, beryllium acetylacetonate, indium acetylacetonate, gallium acetylacetonate, chromium acetylacetonate, hafnium acetylacetonate, ferrous acetylacetonate, lithium acetylacetonate, strontium acetylacetonate hydrate, manganese acetylacetonate, zinc acetylacetonate, β -diketone europium complexes, β -diketone manganese complexes, β -diketone titanium complexes and β -diketone chromium complexes.
According to a preferred embodiment of the present invention, the filler has a particle size of 1 to 100nm, and preferably includes one or more of calcium carbonate, talc, barium sulfate, silica, zinc oxide, titanium oxide, aluminum borate whisker, alumina, sodium antimonate, antimony trioxide, apatite, attapulgite, barium metaborate, barium titanate, bentonite, bismuth oxide, boron oxide, calcium hydroxide, calcium sulfate, carbon black, ceramic microspheres, clay, diatomaceous earth, feldspar, calcium silicate hydrate, magnesium oxide, magnesium hydroxide, molybdenum disulfide, zinc borate, and zinc sulfide.
According to a preferred embodiment of the present invention, the acid anhydride comprises one or more of phthalic anhydride, tetrahydrophthalic anhydride, glycerol trimellitate, polyazelaic anhydride, polysebacic anhydride, elaeostearic anhydride, chlorendic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, diphenyl ether tetracarboxylic dianhydride, cyclopentaderic dianhydride, methylnadic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.
The selected anhydride compound has good heat resistance and can play a good role of a curing agent.
According to a preferred embodiment of the present invention, the coupling agent comprises one or more of gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane.
The surface of the filler, particularly the nano silicon dioxide, is modified by the coupling agent, so that the dispersibility of the filler in epoxy resin, particularly organosilicon modified epoxy resin, is improved, meanwhile, the compatibility of the filler and the epoxy resin, particularly the compatibility of the nano silicon dioxide and the organosilicon modified epoxy resin, the nano filler can effectively improve the crosslinking density of the epoxy resin, the heat resistance and the impact property of the composite material are improved, the water absorption is reduced, in addition, the nano filler can enter gaps of the layered silicate to play a supporting role, the layered silicate is uniformly distributed and has stable layer spacing, and no gap between every two layers is too close, so that a proper water vapor blocking effect can be obtained under the condition of the minimum addition amount.
According to a preferred embodiment of the present invention, the component a comprises the following components in parts by weight: 100 parts of epoxy resin, 0.01-5 parts of antioxidant, 0.01-10 parts of accelerator A, 1-100 parts of filler and 1-100 parts of modified layered silicate; and/or the component B comprises the following components in parts by weight: 100 parts of acid anhydride, 0.01-10 parts of accelerator B and 0.01-5 parts of coupling agent.
According to another aspect of the present invention, a method for preparing the epoxy resin encapsulating adhesive is provided, which includes the following steps:
s1, mixing epoxy resin, an antioxidant, an accelerator A, a filler and modified phyllosilicate to prepare a component A;
s2, mixing anhydride, an accelerator B and a coupling agent to prepare a component B;
and S3, respectively storing the component A and the component B.
According to a preferred embodiment of the present invention, step S1 includes:
preparing epoxy resin, an antioxidant, an accelerator A, a filler and modified phyllosilicate according to parts by weight; then, the components are uniformly mixed to prepare the component A.
According to a preferred embodiment of the present invention, step S2 includes:
preparing acid anhydride, an accelerator B and a coupling agent according to parts by weight; then, the components are uniformly mixed to prepare the component B.
According to the preferred embodiment of the invention, the component A and the component B of the epoxy resin packaging adhesive are respectively stored, and when the epoxy resin packaging adhesive is used, the component A and the component B are mixed according to a proportion and defoamed to obtain the epoxy resin packaging adhesive for packaging.
According to another aspect of the invention, an application of the epoxy resin packaging adhesive is provided, in particular to the application in the field of LED packaging.
According to some embodiments of the invention, the applying comprises: mixing the component A and the component B which are respectively stored according to a proportion, then packaging the obtained mixed product, preferably mixing the component A and the component B which are respectively stored according to a proportion, defoaming and uniformly mixing the mixture, then pouring the glue, packaging and curing.
According to a preferred embodiment of the invention, the encapsulation may take the form of dispensing.
According to a preferred embodiment of the present invention, the curing temperature is 120-160 ℃, and the curing time is 0.5-6 hours.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to these examples.
The analysis method and the performance test method used in the embodiment of the invention are as follows:
(1) high temperature high humidity test
34 lamp beads are respectively packaged by using the packaging glue in the embodiment and the comparative example, the packaged lamp beads absorb moisture for 168 hours under the conditions of 85 ℃ and 85RH percent, then reflow soldering is carried out for 3 times at 260 ℃, and whether the phenomena of glue cracking, degumming and lamp failure occur or not is examined, and the results are shown in table 1.
(2) Water absorption test
The encapsulating adhesives of the examples and comparative examples were cured at 135 c for one hour and then at 150 c for 4 hours, and then films having a length of 4cm, a width of 4cm and a thickness of 2mm were prepared, and left at 120 c under 2MPa for 24 hours, and the water absorption rate was calculated by weighing, and the results are shown in table 1.
(3) Shear strength test
Cut specimens were made of LY16-CZ aluminum alloy, the length and width of the faying surface of the test pieces (cured at 135 ℃ for one hour and then cured at 150 ℃ for 4 hours in examples and comparative examples) were 20mm and 15mm, respectively, the shear test was conducted using an Instron Legend 2367 tensile machine, the tensile rate was set to 5mm/min, and the maximum load and shear strength of the tensile stress were read, and the results are shown in Table 1.
Preparation example 1
(1) 100 parts of sodium bentonite, 3 parts of dodecyl trimethyl ammonium bromide and 200 parts of ultrapure water are put into a beaker and stirred uniformly and then fed into the beakerUltrasonic dispersing with ultrasonic disperser power of 600W, ultrasonic frequency of 40KHz, ultrasonic time of 20min, and temperature of 60 deg.C, oven drying at 80 deg.C, and recording the dried product as α1。
(2) Taking the product α of the step (1)1100 parts of 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl ester 20 parts, xylene 150 parts and acetylacetone chromium 0.5 part are placed in a glass cup and sealed, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 80 ℃, the product is added into a reduced pressure distillation device after dispersion is finished, the constant temperature reaction is carried out for one hour at 80 ℃, xylene solvent is distilled out under reduced pressure, and the obtained product is modified montmorillonite recorded as β1。
Preparation example 2
(1) 100 parts of sodium bentonite, 3 parts of dodecyl trimethyl ammonium bromide and 200 parts of ultrapure water are placed in a beaker, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to be 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to be 60 ℃, the mixture is placed in an oven for drying at 80 ℃ after completion, and the dried product is recorded as α1。
(2) Taking the product α of the step (1)1100 parts of DER-331 epoxy resin, 20 parts of xylene, 150 parts of xylene and 0.5 part of chromium acetylacetonate, placing the mixture into a glass cup, sealing the glass cup, uniformly stirring the mixture, performing ultrasonic dispersion, setting the power of an ultrasonic dispersion instrument to be 600W, the ultrasonic frequency to be 40KHz, the ultrasonic time to be 20min and the temperature to be 80 ℃, adding the product into a reduced pressure distillation device after the dispersion is finished, reacting the product at the constant temperature of 80 ℃ for one hour, and distilling the xylene solvent under reduced pressure to obtain a product, namely modified montmorillonite, which is recorded as β2。
Preparation example 3
(1) 100 parts of sodium bentonite, 3 parts of octadecyl trimethyl ammonium bromide and 200 parts of ultrapure water are placed in a beaker, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 60 ℃, the mixture is placed in an oven for drying at 80 ℃, and the dried product is recorded as α3。
(2) Taking the product α of the step (1)3100 parts of DER-331 epoxy resin, 20 parts of xylene, 150 parts of xylene and 0.5 part of chromium acetylacetonate, placing the mixture into a glass cup, sealing the glass cup, uniformly stirring the mixture, performing ultrasonic dispersion, setting the power of an ultrasonic dispersion instrument to be 600W, the ultrasonic frequency to be 40KHz, the ultrasonic time to be 20min and the temperature to be 80 ℃, adding the product into a reduced pressure distillation device after the dispersion is finished, reacting the product at the constant temperature of 80 ℃ for one hour, and distilling the xylene solvent under reduced pressure to obtain a product, namely modified montmorillonite, which is recorded as β3。
Preparation example 4
(1) 100 parts of sodium bentonite, 3 parts of octadecyl trimethyl ammonium bromide and 200 parts of ultrapure water are placed in a beaker, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 60 ℃, the mixture is placed in an oven for drying at 80 ℃, and the dried product is recorded as α3。
(2) Taking the product α of the step (1)3100 parts of 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl ester 20 parts, xylene 150 parts and acetylacetone chromium 0.5 part are placed in a glass cup and sealed, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 80 ℃, the product is added into a reduced pressure distillation device after dispersion is finished, the constant temperature reaction is carried out for one hour at 80 ℃, xylene solvent is distilled out under reduced pressure, and the obtained product is modified montmorillonite recorded as β4。
Preparation example 5
(1) 100 parts of sodium bentonite, 3 parts of tetradecyl trimethyl ammonium bromide and 200 parts of ultrapure water are placed in a beaker, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 60 ℃, the mixture is placed in an oven for drying at 80 ℃, and the dried product is recorded as α5。
(2) Taking the product α of the step (1)5100 parts of 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl ester 20 parts, 150 parts of xylene and 0.5 part of chromium acetylacetonate are placed in a glass cupSealing, stirring uniformly, and performing ultrasonic dispersion, wherein the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 80 ℃, after the dispersion is finished, adding the product into a reduced pressure distillation device, reacting at the constant temperature of 80 ℃ for one hour, and distilling out a xylene solvent under reduced pressure to obtain a product, namely modified montmorillonite, which is recorded as β5。
Preparation example 6
(1) 100 parts of sodium bentonite, 3 parts of hexadecyl trimethyl ammonium bromide and 200 parts of ultrapure water are placed in a beaker, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to be 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to be 60 ℃, the mixture is placed in an oven for drying at 80 ℃, and the dried product is recorded as α6。
(2) Taking the product α of the step (1)6100 parts of 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl ester 20 parts, xylene 150 parts and acetylacetone chromium 0.5 part are placed in a glass cup and sealed, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 80 ℃, the product is added into a reduced pressure distillation device after dispersion is finished, the constant temperature reaction is carried out for one hour at 80 ℃, xylene solvent is distilled out under reduced pressure, and the obtained product is modified montmorillonite recorded as β6。
Preparation example 7
(1) 100 parts of sodium bentonite, 5 parts of octadecyl trimethyl ammonium bromide and 200 parts of ultrapure water are placed in a beaker, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 60 ℃, the mixture is placed in an oven for drying at 80 ℃, and the dried product is recorded as α7。
(2) Taking the product α of the step (1)7100 parts of 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl ester 20 parts, xylene 150 parts and acetylacetone chromium 0.5 part are placed in a glass cup and sealed, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to be 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to be 80 ℃, and after dispersion is finished, the ultrasonic dispersion instrument is used for dispersingAdding the product into a reduced pressure distillation device, reacting for one hour at a constant temperature of 80 ℃, and distilling out the xylene solvent under reduced pressure to obtain a product, namely the modified montmorillonite, which is recorded as β7。
Preparation example 8
(1) 100 parts of sodium bentonite, 1 part of octadecyl trimethyl ammonium bromide and 200 parts of ultrapure water are placed in a beaker, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 60 ℃, the mixture is placed in an oven for drying at 80 ℃, and the dried product is recorded as α8。
(2) Taking the product α of the step (1)8100 parts of 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl ester 20 parts, xylene 150 parts and acetylacetone chromium 0.5 part are placed in a glass cup and sealed, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 80 ℃, the product is added into a reduced pressure distillation device after dispersion is finished, the constant temperature reaction is carried out for one hour at 80 ℃, xylene solvent is distilled out under reduced pressure, and the obtained product is modified montmorillonite recorded as β8。
Preparation example 9
(1) Putting 100 parts of bentonite, 3 parts of octadecyl trimethyl ammonium bromide and 200 parts of ultrapure water into a beaker, uniformly stirring, performing ultrasonic dispersion, setting the power of an ultrasonic dispersion instrument to be 600W, the ultrasonic frequency to be 40KHz, the ultrasonic time to be 20min and the temperature to be 60 ℃, putting the beaker into an oven to be dried at 80 ℃, and recording the dried product as α9。
(2) Taking the product α of the step (1)9100 parts of 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl ester 20 parts, xylene 150 parts and acetylacetone chromium 0.5 part are placed in a glass cup and sealed, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 80 ℃, the product is added into a reduced pressure distillation device after dispersion is finished, the constant temperature reaction is carried out for one hour at 80 ℃, xylene solvent is distilled out under reduced pressure, and the obtained product is modified montmorillonite recorded as β9。
Preparation example 10
(1) 100 parts of sodium bentonite, 3 parts of octadecyl trimethyl ammonium bromide and 200 parts of ultrapure water are placed in a beaker, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 60 ℃, the mixture is placed in an oven for drying at 80 ℃, and the dried product is recorded as α3。
(2) Taking the product α of the step (1)3100 parts of EPSI-3210 epoxy resin, 20 parts of xylene, 150 parts of xylene and 0.5 part of chromium acetylacetonate, placing the mixture in a glass cup, sealing, uniformly stirring, performing ultrasonic dispersion, setting the power of an ultrasonic dispersion instrument to be 600W, the ultrasonic frequency to be 40KHz, the ultrasonic time to be 20min and the temperature to be 80 ℃, adding the product into a reduced pressure distillation device after the dispersion is finished, reacting for one hour at constant temperature of 80 ℃, and distilling the xylene solvent under reduced pressure to obtain a product, namely modified montmorillonite, which is recorded as β10。
Preparation example 11
(1) 100 parts of sodium bentonite, 3 parts of octadecyl trimethyl ammonium bromide and 200 parts of ultrapure water are placed in a beaker, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is set to 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is set to 60 ℃, the mixture is placed in an oven for drying at 80 ℃, and the dried product is recorded as α3。
(2) Taking the product α of the step (1)3100 parts of EPSI-6878 epoxy resin, 150 parts of dimethylbenzene and 0.5 part of chromium acetylacetonate, placing the materials into a glass cup, sealing, uniformly stirring, performing ultrasonic dispersion, setting the power of an ultrasonic dispersion instrument to be 600W, the ultrasonic frequency to be 40KHz, the ultrasonic time to be 20min and the temperature to be 80 ℃, adding the product into a reduced pressure distillation device after the dispersion is finished, reacting for one hour at constant temperature of 80 ℃, distilling the dimethylbenzene solvent under reduced pressure, and obtaining a product which is modified montmorillonite recorded as β11。
Preparation example 12
(1) 100 parts of sodium bentonite, 3 parts of octadecyl trimethyl ammonium bromide and 200 parts of ultrapure water are put into a beaker, stirred uniformly and then subjected to ultrasonic dispersion, and the power of an ultrasonic dispersion instrumentSetting the ultrasonic frequency at 40KHz for 20min at 60 deg.C, drying in oven at 80 deg.C to obtain α3。
(2) Taking the product α of the step (1)3100 parts of 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl ester 20 parts, xylene 150 parts and β -diketone manganese complex 0.5 part are placed in a glass cup and sealed, ultrasonic dispersion is carried out after uniform stirring, the power of an ultrasonic dispersion instrument is 600W, the ultrasonic frequency is 40KHz, the ultrasonic time is 20min, the temperature is 80 ℃, the product is added into a reduced pressure distillation device after dispersion is finished, the constant temperature reaction is carried out for one hour at 80 ℃, xylene solvent is distilled out under reduced pressure, and the obtained product is modified montmorillonite which is marked as β12。
Comparative example 1
Preparing a component A: 70 parts of 3, 4-epoxy cyclohexyl methyl formate-3 ',4' -epoxy cyclohexyl methyl ester, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 1 part of 2, 6-tertiary butyl-4-methylphenol, 0.5 part of triphenyl phosphite, 0.5 part of triphenylphosphine and 3 parts of spherical nano silicon dioxide (50nm) are stirred for 1 hour at the temperature of 80 +/-5 ℃ until the components are uniformly mixed.
Preparing a component B: 70 parts of methyl hexahydrophthalic anhydride, 30 parts of hexahydrophthalic anhydride, 2 parts of N- (2-cyanoethyl) caprolactam, 1 part of neopentyl glycol and 0.1 part of gamma-mercaptopropyl trimethoxy silane are stirred for 1 hour at the temperature of 80 +/-5 ℃ until the mixture is uniformly mixed.
Respectively storing the component A and the component B;
preparing epoxy resin packaging adhesive: according to the mass ratio A: b is 100: 75, mixing the component A and the component B, and performing centrifugal deaeration and uniform mixing to obtain the required epoxy resin packaging adhesive. And packaging the LED lamp beads by using the obtained packaging adhesive, and curing for 4 hours at 150 ℃ after curing for one hour at 135 ℃.
Comparative example 2
Preparing a component A: 70 parts of 3, 4-epoxy cyclohexyl methyl formate-3 ',4' -epoxy cyclohexyl methyl ester, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 1 part of 2, 6-tertiary butyl-4-methylphenol, 0.5 part of triphenyl phosphite, 0.5 part of triphenylphosphine and 3 parts of spherical nano silicon dioxide (50nm) are stirred for 1 hour at the temperature of 80 +/-5 ℃ until the components are uniformly mixed.
Preparing a component B: 70 parts of methyl hexahydrophthalic anhydride, 30 parts of hexahydrophthalic anhydride, 2 parts of N- (2-cyanoethyl) caprolactam, 1 part of neopentyl glycol and 0.1 part of gamma-mercaptopropyl trimethoxy silane are stirred for 1 hour at the temperature of 80 +/-5 ℃ until the mixture is uniformly mixed.
Respectively storing the component A and the component B;
preparing epoxy resin packaging adhesive: according to the mass ratio A: b is 100: 85, mixing the component A and the component B, and performing centrifugal deaeration and uniform mixing to obtain the required epoxy resin packaging adhesive. And packaging the LED lamp beads by using the obtained packaging adhesive, and curing for 4 hours at 150 ℃ after curing for one hour at 135 ℃.
Comparative example 3
The component A is prepared from 70 parts of 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl ester, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 1 part of 2, 6-tertiary butyl-4-methylphenol, 0.5 part of triphenyl phosphite, 0.5 part of triphenylphosphine, 3 parts of spherical nano silicon dioxide (50nm) and a product α110 parts of the mixture are stirred for 1 hour at the temperature of 80 plus or minus 5 ℃ until the mixture is uniform.
Preparing a component B: 70 parts of methyl hexahydrophthalic anhydride, 30 parts of hexahydrophthalic anhydride, 2 parts of N- (2-cyanoethyl) caprolactam, 1 part of neopentyl glycol and 0.1 part of gamma-mercaptopropyl trimethoxy silane are stirred for 1 hour at the temperature of 80 +/-5 ℃ until the mixture is uniformly mixed.
Respectively storing the component A and the component B;
preparing epoxy resin packaging adhesive: according to the mass ratio A: b is 100: 85, mixing the component A and the component B, and performing centrifugal deaeration and uniform mixing to obtain the required epoxy resin packaging adhesive. And packaging the LED lamp beads by using the obtained packaging adhesive, and curing for 4 hours at 150 ℃ after curing for one hour at 135 ℃.
Example 1
Preparing a component A: 70 parts of 3, 4-epoxy cyclohexyl methyl formate-3 ',4' -epoxy cyclohexyl methyl ester, 20 parts of DER-331 epoxy resin, 10 parts of DER-144 epoxy resin, 1 part of 2, 6-tertiary butyl-4-methyl phenol, 0.5 part of triphenyl phosphite, 0.5 part of triphenylphosphine, 3 parts of spherical nano silicon dioxide (50nm) and modified montmorilloniteSoil β110 parts of the mixture are stirred for 1 hour at the temperature of 80 plus or minus 5 ℃ until the mixture is uniform.
Preparing a component B: 70 parts of methyl hexahydrophthalic anhydride, 30 parts of hexahydrophthalic anhydride, 2 parts of N- (2-cyanoethyl) caprolactam, 1 part of neopentyl glycol and 0.1 part of gamma-mercaptopropyl trimethoxy silane are stirred for 1 hour at the temperature of 80 +/-5 ℃ until the mixture is uniformly mixed.
Respectively storing the component A and the component B;
preparing epoxy resin packaging adhesive: according to the mass ratio A: b is 100: 85, mixing the component A and the component B, and performing centrifugal deaeration and uniform mixing to obtain the required epoxy resin packaging adhesive. And packaging the LED lamp beads by using the obtained packaging adhesive, and curing for 4 hours at 150 ℃ after curing for one hour at 135 ℃.
Examples 2 to 12
Same as example 1, except that modified montmorillonite β1Respectively replaced by modified montmorillonite β2-modified montmorillonite β12。
Comparative example 4
Preparing a component A: stirring 70 parts of 3, 4-epoxy cyclohexyl methyl formate-3 ',4' -epoxy cyclohexyl methyl ester, 30 parts of EPSI-3201 organic silicon modified epoxy resin, 1 part of 2, 6-tertiary butyl-4-methyl phenol, 0.5 part of triphenyl phosphite, 0.5 part of triphenylphosphine and 3 parts of spherical nano silicon dioxide (50nm) at the temperature of 80 +/-5 ℃ for 1 hour until the components are uniformly mixed.
Preparing a component B: 70 parts of methyl hexahydrophthalic anhydride, 30 parts of hexahydrophthalic anhydride, 2 parts of N- (2-cyanoethyl) caprolactam, 1 part of neopentyl glycol and 0.1 part of gamma-mercaptopropyl trimethoxy silane are stirred for 1 hour at the temperature of 80 +/-5 ℃ until the mixture is uniformly mixed.
Respectively storing the component A and the component B
Preparing epoxy resin packaging adhesive: according to the mass ratio A: b is 100: 65, mixing the component A and the component B, and performing centrifugal deaeration and uniform mixing to obtain the required epoxy resin packaging adhesive. And packaging the LED lamp beads by using the obtained packaging adhesive, and curing for 4 hours at 150 ℃ after curing for one hour at 135 ℃.
Example 13
Preparing a component A: 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl70 parts of ester, 30 parts of EPSI-3201 organosilicon epoxy resin, 1 part of 2, 6-tertiary butyl-4-methylphenol, 0.5 part of triphenyl phosphite, 0.5 part of triphenylphosphine, 3 parts of spherical nano silicon dioxide (50nm), and modified montmorillonite β410 parts of the mixture are stirred for 1 hour at the temperature of 80 plus or minus 5 ℃ until the mixture is uniform.
Preparing a component B: 70 parts of methyl hexahydrophthalic anhydride, 30 parts of hexahydrophthalic anhydride, 2 parts of N- (2-cyanoethyl) caprolactam, 1 part of neopentyl glycol and 0.1 part of gamma-mercaptopropyl trimethoxy silane are stirred for 1 hour at the temperature of 80 +/-5 ℃ until the mixture is uniformly mixed.
Respectively storing the component A and the component B
Preparing epoxy resin packaging adhesive: according to the mass ratio A: b is 100: 65, mixing the component A and the component B, and performing centrifugal deaeration and uniform mixing to obtain the required epoxy resin packaging adhesive. And packaging the LED lamp beads by using the obtained packaging adhesive, and curing for 4 hours at 150 ℃ after curing for one hour at 135 ℃.
The performance of the encapsulation adhesive of the above examples and comparative examples is shown in the following table:
table 1: performance test meter
| Cracking rubber% | Degummed% | Dead light% | Water absorption/%) | Shear strength (MPa) | |
| Comparative example 1 | 5 | 0 | 15 | 0.43 | 8.9 |
| Comparative example 2 | 4.8 | 0 | 14.5 | 0.44 | 9.1 |
| Comparative example 3 | 6.1 | 0 | 14.9 | 0.35 | 7.8 |
| Example 1 | 0 | 0 | 0 | 0.27 | 16 |
| Example 2 | 0 | 0 | 0 | 0.25 | 14.5 |
| Example 3 | 0 | 0 | 0 | 0.24 | 14.5 |
| Example 4 | 0 | 0 | 0 | 0.25 | 16.1 |
| Example 5 | 0 | 0 | 0 | 0.26 | 15.6 |
| Example 6 | 0 | 0 | 0 | 0.26 | 15.8 |
| Example 7 | 0 | 0 | 0 | 0.24 | 17.1 |
| Example 8 | 0 | 0 | 0 | 0.29 | 12 |
| Example 9 | 0 | 0 | 0 | 0.30 | 15.3 |
| Example 10 | 0 | 0 | 0 | 0.24 | 16.5 |
| Example 11 | 0 | 0 | 0 | 0.24 | 16.3 |
| Example 12 | 0 | 0 | 0 | 0.26 | 15.6 |
| Comparative example 4 | 2 | 0 | 6 | 0.36 | 11.4 |
| Example 13 | 0 | 0 | 0 | 0.18 | 18.3 |
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
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. An epoxy resin packaging adhesive comprises a component A and a component B; the component A comprises the following components: epoxy resin, antioxidant, accelerator A, filler and modified phyllosilicate; the component B comprises the following components: acid anhydride, accelerator B and coupling agent; preferably, the mass ratio of the component A to the component B is 1: (0.2-1.2).
2. The epoxy resin encapsulating adhesive according to claim 1, wherein the modified phyllosilicate is prepared by a method comprising the steps of:
1) intercalation treatment is carried out on the layered silicate by using an organic intercalation agent to obtain an intercalation product;
2) and modifying the intercalation product by using epoxy resin to obtain the modified phyllosilicate.
3. The epoxy resin encapsulating adhesive according to claim 1 or 2, wherein the layered silicate comprises one or more of pyrophyllite, zeolite powder, attapulgite, talc, mica, kaolin, bentonite, serpentine powder, chlorite powder, and montmorillonite; and/or the organic intercalating agent comprises an alkyl quaternary ammonium salt, preferably a C12-18 alkyl quaternary ammonium salt, more preferably one or more of dodecyl trimethyl ammonium halide, tetradecyl trimethyl ammonium halide, hexadecyl trimethyl ammonium halide, octadecyl bis-hydroxyethyl methyl ammonium halide, dodecyl dimethyl benzyl ammonium halide, tetradecyl dimethyl benzyl ammonium halide, hexadecyl dimethyl benzyl ammonium halide, and octadecyl dimethyl benzyl ammonium halide.
4. The epoxy resin encapsulating glue according to any one of claims 1-3, wherein the step 2) comprises:
2A) carrying out ultrasonic treatment on a mixture containing an intercalation product, epoxy resin, an accelerant C and a solvent to obtain an ultrasonic product;
2B) removing the solvent in the ultrasonic product obtained in the step 2A) to obtain the modified phyllosilicate.
5. The epoxy resin encapsulating glue of any one of claims 1-4, wherein the epoxy resin comprises 2, 3-epoxypropyl acrylate, bis (3, 4-epoxycyclohexylmethyl) adipate, 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, 3, 4-epoxy-6-methylcyclohexanecarboxylic acid-3 ',4' -epoxy-6 ' -methylcyclohexanemethyl ester, dicyclopentadiene diepoxy, bis- (2, 3-epoxycyclopentyl) -ether, 3, 4-epoxycyclohexylmethyl-2 ',3' -epoxycyclohexyl ether, bis- (2, 3-epoxycyclohexane), 1, 2-bis- (2, 3-epoxycyclohexyloxy) -ethane, bis- (2, 3-epoxycyclohexyl) ether, 1-bis (2',3' -epoxycyclohexyloxymethyl) -3, 4-epoxycyclohexane, diglycidyl phthalate, 4-dihydroxydiphenylsulfone bisglycidyl ether, tetraphenolethane tetraglycidyl ether, resorcinol bisglycidyl ether, phloroglucinol glycidyl ether, one or more of resorcinol acetal tetraglycidyl ether, p-aminophenol epoxy resin, 4' -diaminodiphenylmethane tetraglycidyl amine, 1, 2-epoxycyclohexane-4, 5-dicarboxylic acid epoxy resin, tetrahydrobenzene dimethyl ester epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and organosilicon modified epoxy resin; and/or the antioxidant comprises octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-tert-butyl-4-methylphenol, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, pentaerythritol tetrakis (beta- (3, 5-tert-butyl-4-methylphenyl) propionate), spiroglycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], 2-ethylidenebis (4, 6-di-tert-butylbenzene) fluorophosphite, triphenyl phosphite, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, trioctyl, tridecyl ester, tridodecyl alcohol ester, One or more of tricetyl alcohol ester, diphenylamine, p-phenylenediamine, and dihydroquinoline.
6. The epoxy resin encapsulating adhesive according to any one of claims 1 to 5, wherein the accelerator A, the accelerator B and the accelerator C may be the same or different;
preferably, the accelerator a comprises one or more of acetylacetone metal salts, beta-diketone metal complexes, ethyltriphenyl phosphonium iodide, and triphenylphosphine, preferably comprising one or more of cobalt acetylacetonate hydrate, beryllium acetylacetonate, indium acetylacetonate, gallium acetylacetonate, chromium acetylacetonate, hafnium acetylacetonate, ferrous acetylacetonate, lithium acetylacetonate, strontium acetylacetonate hydrate, manganese acetylacetonate, zinc acetylacetonate, beta-diketone europium complexes, beta-diketone manganese complexes, beta-diketone titanium complexes, and beta-diketone chromium complexes;
preferably, the accelerator B comprises one or more of N- (2-cyanoethyl) caprolactam, diethylenetriamine, triethylene tetramine, polyethylene polyamine, tetramethyl ammonium bromide, tetraethyl ammonium bromide or tetrabutyl ammonium bromide, N-p-chlorophenyl-N ', N' -dimethyl urea, dimethyl imidazole urea, 2-ethyl-4-methyl imidazole, boron trifluoride amine complex, composite nano titanium dioxide, benzyl dimethylamine, pyridine, trimethylamine, triethylamine, triethanolamine, N, N-dimethylaniline, triethylamine, triethanolamine, dimethylethanolamine, propylene glycol, glycerol, neopentyl glycol;
preferably, the promoter C comprises one or more of acetylacetone metal salts, β -diketone metal complexes, ethyltriphenyl phosphonium iodide, and triphenylphosphine, preferably comprising one or more of cobalt acetylacetonate hydrate, beryllium acetylacetonate, indium acetylacetonate, gallium acetylacetonate, chromium acetylacetonate, hafnium acetylacetonate, ferrous acetylacetonate, lithium acetylacetonate, strontium acetylacetonate hydrate, manganese acetylacetonate, zinc acetylacetonate, β -diketone europium complexes, β -diketone manganese complexes, β -diketone titanium complexes, and β -diketone chromium complexes; and/or the presence of a gas in the gas,
the particle size of the filler is 1-100nm, and preferably comprises one or more of calcium carbonate, talcum powder, barium sulfate, silicon dioxide, zinc oxide, titanium oxide, aluminum borate whisker, aluminum oxide, sodium antimonate, antimony trioxide, apatite, attapulgite, barium metaborate, barium titanate, bentonite, bismuth oxide, boron oxide, calcium hydroxide, calcium sulfate, carbon black, ceramic microspheres, clay, diatomite, feldspar, calcium silicate hydrate, magnesium oxide, magnesium hydroxide, molybdenum disulfide, zinc borate and zinc sulfide; and/or the presence of a gas in the gas,
the acid anhydride comprises one or more of phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride glyceride, polyazelaic anhydride, polysebacic anhydride, elaeostearic anhydride, chlorendic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, diphenyl ether tetracarboxylic anhydride, cyclopentyltetracarboxylic anhydride, methylnadic anhydride, hexahydrophthalic anhydride and methyl hexahydrophthalic anhydride; and/or the coupling agent comprises one or more of gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane.
7. The epoxy resin encapsulating glue according to any one of claims 1-6, wherein the A component comprises the following components in parts by weight: 100 parts of epoxy resin, 0.01-5 parts of antioxidant, 0.01-10 parts of accelerator A, 1-100 parts of filler and 1-100 parts of modified layered silicate; and/or the component B comprises the following components in parts by weight: 100 parts of acid anhydride, 0.01-10 parts of accelerator B and 0.01-5 parts of coupling agent.
8. The method for preparing an epoxy resin encapsulating glue according to any one of claims 1-7, comprising the steps of:
s1, mixing epoxy resin, an antioxidant, an accelerator A, a filler and modified phyllosilicate to prepare a component A;
s2, mixing anhydride, an accelerator B and a coupling agent to prepare a component B;
and S3, respectively storing the component A and the component B.
9. Use of an epoxy resin encapsulating glue according to any one of claims 1-7 or prepared according to the method of claim 8, in particular in the field of LED encapsulation.
10. The application according to claim 9, wherein the application comprises: mixing the separately stored component A and component B in proportion, and packaging the obtained mixed product.
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| CN202010334972.XA CN111534260B (en) | 2020-04-24 | 2020-04-24 | Epoxy resin packaging adhesive and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286770A (en) * | 2022-08-11 | 2022-11-04 | 国科广化(南雄)新材料研究院有限公司 | Curing agent based on phenol-urethane bond and preparation method and application thereof |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4889885A (en) * | 1987-03-04 | 1989-12-26 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composite material containing a layered silicate |
| JPH04154884A (en) * | 1990-10-19 | 1992-05-27 | Hitachi Chem Co Ltd | Flexible adhesive |
| US5853886A (en) * | 1996-06-17 | 1998-12-29 | Claytec, Inc. | Hybrid nanocomposites comprising layered inorganic material and methods of preparation |
| CN1250064A (en) * | 1998-10-06 | 2000-04-12 | 中国科学院化学研究所 | Preparation of epoxy resin/montmorillonoid intercalation composite material |
| US6057396A (en) * | 1996-12-06 | 2000-05-02 | Amcol International Corporation | Intercalates formed by co-intercalation of monomer, oligomer or polymer intercalants and surface modifier intercalants and layered materials and nonocomposites prepared with the intercalates |
| US6251980B1 (en) * | 1996-12-06 | 2001-06-26 | Amcol International Corporation | Nanocomposites formed by onium ion-intercalated clay and rigid anhydride-cured epoxy resins |
| CN1405231A (en) * | 2001-09-18 | 2003-03-26 | 财团法人工业技术研究院 | Modified laminated clay and epoxy resin/clay nano composite material comprising said clay |
| CN1575316A (en) * | 2001-10-23 | 2005-02-02 | 阿什兰公司 | Thermosetting inorganic clay nanodispersions and their use |
| US20070197710A1 (en) * | 2004-09-17 | 2007-08-23 | Wu Wen P | Polymer Articles With Treated Fillers And Products And Methods Of Using Same |
| CN102146197A (en) * | 2011-04-20 | 2011-08-10 | 东华大学 | Method for preparing nanomontmorillonite intercalated epoxy resin exfoliated composite material |
| CN102533194A (en) * | 2012-02-21 | 2012-07-04 | 广州秀珀化工股份有限公司 | Layered silicate intercalation composite adhesive for wind-driven generator blade and preparation method thereof |
| CN103131373A (en) * | 2013-03-20 | 2013-06-05 | 苏州太湖电工新材料股份有限公司 | Composite adhesive for single-sided film reinforced little glue mica tape and preparation method thereof |
| CN103146329A (en) * | 2011-12-07 | 2013-06-12 | 南京工程学院 | Preparation method for epoxy adhesive modified by surface-modified nanoparticles |
| CN103665758A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Modified epoxy resin system for carbon fiber boards for pultrusion structure reinforcement |
| CN104804688A (en) * | 2015-04-21 | 2015-07-29 | 汕头市骏码凯撒有限公司 | Outdoor LED packing matt epoxy resin package adhesive and preparation method thereof |
| CN109679289A (en) * | 2018-12-28 | 2019-04-26 | 华东理工大学 | A kind of preparation method and composite material of high-toughness wear-resistant epoxy resin composite material |
-
2020
- 2020-04-24 CN CN202010334972.XA patent/CN111534260B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4889885A (en) * | 1987-03-04 | 1989-12-26 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composite material containing a layered silicate |
| JPH04154884A (en) * | 1990-10-19 | 1992-05-27 | Hitachi Chem Co Ltd | Flexible adhesive |
| US5853886A (en) * | 1996-06-17 | 1998-12-29 | Claytec, Inc. | Hybrid nanocomposites comprising layered inorganic material and methods of preparation |
| US6057396A (en) * | 1996-12-06 | 2000-05-02 | Amcol International Corporation | Intercalates formed by co-intercalation of monomer, oligomer or polymer intercalants and surface modifier intercalants and layered materials and nonocomposites prepared with the intercalates |
| US6251980B1 (en) * | 1996-12-06 | 2001-06-26 | Amcol International Corporation | Nanocomposites formed by onium ion-intercalated clay and rigid anhydride-cured epoxy resins |
| CN1250064A (en) * | 1998-10-06 | 2000-04-12 | 中国科学院化学研究所 | Preparation of epoxy resin/montmorillonoid intercalation composite material |
| CN1405231A (en) * | 2001-09-18 | 2003-03-26 | 财团法人工业技术研究院 | Modified laminated clay and epoxy resin/clay nano composite material comprising said clay |
| CN1575316A (en) * | 2001-10-23 | 2005-02-02 | 阿什兰公司 | Thermosetting inorganic clay nanodispersions and their use |
| US20070197710A1 (en) * | 2004-09-17 | 2007-08-23 | Wu Wen P | Polymer Articles With Treated Fillers And Products And Methods Of Using Same |
| CN102146197A (en) * | 2011-04-20 | 2011-08-10 | 东华大学 | Method for preparing nanomontmorillonite intercalated epoxy resin exfoliated composite material |
| CN103146329A (en) * | 2011-12-07 | 2013-06-12 | 南京工程学院 | Preparation method for epoxy adhesive modified by surface-modified nanoparticles |
| CN102533194A (en) * | 2012-02-21 | 2012-07-04 | 广州秀珀化工股份有限公司 | Layered silicate intercalation composite adhesive for wind-driven generator blade and preparation method thereof |
| CN103665758A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Modified epoxy resin system for carbon fiber boards for pultrusion structure reinforcement |
| CN103131373A (en) * | 2013-03-20 | 2013-06-05 | 苏州太湖电工新材料股份有限公司 | Composite adhesive for single-sided film reinforced little glue mica tape and preparation method thereof |
| CN104804688A (en) * | 2015-04-21 | 2015-07-29 | 汕头市骏码凯撒有限公司 | Outdoor LED packing matt epoxy resin package adhesive and preparation method thereof |
| CN109679289A (en) * | 2018-12-28 | 2019-04-26 | 华东理工大学 | A kind of preparation method and composite material of high-toughness wear-resistant epoxy resin composite material |
Non-Patent Citations (3)
| Title |
|---|
| G. I. GURINA 等: "MONTMORILLONITE INTERCALATION COMPLEXES AND THEIR INTERACTION WITH EPOXY COMPOUNDS", 《TEORETICHESKAYA I T~KSPERIMENTAL"NAYA KHIMIYA》 * |
| 郭宁等: "环氧树脂/有机蒙脱土纳米复合材料的制备与表征", 《绝缘材料》 * |
| 陈斌 等: "剥离型环氧树脂/粘土纳米复合材料热/力学性能", 《高分子材料科学与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286770A (en) * | 2022-08-11 | 2022-11-04 | 国科广化(南雄)新材料研究院有限公司 | Curing agent based on phenol-urethane bond and preparation method and application thereof |
| CN115286770B (en) * | 2022-08-11 | 2024-01-09 | 国科广化(南雄)新材料研究院有限公司 | Curing agent based on phenol-carbamate bond, and preparation method and application thereof |
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