CN101916816A - A kind of light-emitting diode and its preparation method - Google Patents

Abstract

The invention discloses a light-emitting diode (LED). The LED at least comprises a bracket, an LED chip and a light-emitting layer arranged on the LED chip and is characterized in that: the light-emitting layer is a mixed system of one or more kinds of fluorescent powder capable of sending out light with various colors and an adhesive requiring double curing; and the adhesive is an adhesive of a double curing system consisting of ultraviolet curing-thermocuring, ultraviolet curing-microwave curing, ultraviolet curing-anaerobic curing or ultraviolet curing-electron beam curing. The light-emitting layer solves the problems of colloid solidification and fluorescent powder sedimentation in the process of coating the fluorescent powder, so the LED has the advantages of improving the uniformity of the fluorescent powder on the chip, enhancing the adhesive property between the light-emitting layer and the chip and shortening the curing time of the light-emitting layer.

Description

A kind of light-emitting diode and its preparation method

technical field

The invention relates to the technical field of optoelectronic devices, in particular to a light emitting diode and a preparation method thereof.

Background technique

Light Emitting Diode (LED for short) is a light-emitting device that emits ultraviolet, visible or infrared light when a forward voltage is applied across a semiconductor p-n junction. It is a new generation of solid-state light source. Because of its small size, long life, low driving voltage, fast response, shock resistance, heat resistance and other characteristics, since the first light-emitting diode came out in 1964, people have not stopped the pace of research and development. With the development of light-emitting materials The development and improvement of semiconductor manufacturing process, as well as the introduction of distributed Bragg reflection structure, optical microcavity and quantum well structure in the chip growth process, have continuously improved the efficiency of light-emitting diodes for semiconductor lighting in recent years.

With the rapid development of the LED industry, the application range of high-efficiency LEDs is gradually expanding, and correspondingly higher requirements are increasingly put forward for their performance, including brightness, color rendering performance, and light and color consistency. Improvement of LED performance needs to focus on the coating of phosphor, in order to solve the problems of gel solidification, uneven dispersion of phosphor in colloid and phosphor precipitation in the dispensing process, the equipment used for dispensing phosphor, the container for glue, etc. All need to maintain a certain temperature and constant stirring, but these problems have not been well resolved. Therefore, how to solve the problems of colloidal solidification, uneven dispersion of phosphors in the colloid, and deposition of phosphors during the dispensing process is very important for improving the performance of LEDs, and even prolonging their service life, as well as promoting the sustainable development of the entire industry. significance.

Contents of the invention

The technical problem to be solved by the present invention is how to provide a light-emitting diode and its preparation method. This solution solves the problems of colloid solidification and phosphor easy to precipitate in the colloid in the process of coating phosphor powder, and improves the glue output during the dispensing process. The uniformity of the light-emitting layer increases the consistency of the light-emitting layer in the light-emitting diode, increases the bonding degree between the light-emitting layer and the chip, and reduces the time required for curing the light-emitting layer; the solution is simple and effective, and can greatly reduce the production cost of the device and process difficulty, greatly improving the yield rate of related devices.

The technical problem proposed by the present invention is solved as follows: provide a light-emitting diode, at least including a bracket, an LED chip and a light-emitting layer on the LED chip, characterized in that the material of the light-emitting layer is one or more kinds of light-emitting materials. A mixed system composed of fluorescent powders of various colors and adhesives that require dual curing. The dual curing is completed through two independent curing stages, one of which is through UV curing reaction and the other is dark reaction. The adhesives requiring dual curing include UV curing-thermal curing system, UV curing-microwave curing system, UV curing-anaerobic curing system and UV curing-electron beam curing system:

① Radical UV curing-thermal curing system, the raw materials include the following components by weight:

Unsaturated polyester resin or acrylic resin or polythiol-polyene 30-40 parts

Epoxy resin or isocyanate or amino resin or free radical thermal curing agent 45 parts

Styrene and its derivatives or monofunctional or polyfunctional acrylic acid 0.2-3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

The curing process is: UV curing first, then heating and curing, and then UV curing; or heating and curing first, then UV curing, and then heating and curing;

② Radical UV curing-microwave curing system, the raw materials include the following components by weight:

Unsaturated polyester resin or acrylic resin or polythiol-polyene 30-40 parts

Epoxy resin or isocyanate or amino resin or free radical thermal curing agent 35-45 parts

Styrene and its derivatives or monofunctional or polyfunctional acrylic acid 0.2-3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

The curing process is: UV curing first, then microwave curing, and then UV curing; or microwave curing first, then UV curing, and then heating or microwave curing;

③ Radical UV curing-anaerobic curing system, the raw materials include the following components by weight:

Unsaturated polyester resin or acrylic resin or polythiol-polyene 55-65 parts

Dimethacrylate polyol ester or bisphenol A epoxy polyol ester 20-30 parts

Styrene and its derivatives or monofunctional or polyfunctional acrylic acid 0.2-3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

The curing process is: firstly carry out ultraviolet light curing, then the adhesive part which is not exposed to light and under anoxic conditions will automatically undergo anaerobic curing reaction, and then carry out ultraviolet light curing;

④ Radical UV curing-electron beam curing system, the raw materials include the following components by weight:

Unsaturated polyester resin or acrylic resin or polythiol-polyene 35-40 parts

Bisphenol A vinyl ester resin, etc. 50-55 parts

Styrene and its derivatives or monofunctional or multifunctional acrylic acid 0.2 to 3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

The curing process is: first UV curing, then electron beam curing under vacuum, and then UV curing;

⑤ Cationic UV curing-heat curing system, raw materials include the following components by weight:

Epoxy resin or modified epoxy resin 35-45 parts

Epoxy resin or isocyanate or amino resin or free radical thermal curing agent 40-45 parts

Thinner 0.4～9 parts

Cationic photoinitiator 0.1 to 3 parts

Photosensitizers and additives 0.2 to 3 parts

The curing process is: UV curing first, then heating and curing, and then UV curing; or heating and curing first, then UV curing, and then heating and curing;

⑥ Cationic UV curing-microwave curing system, the raw materials include the following components by weight:

Epoxy resin or modified epoxy resin 35-45 parts

Epoxy resin or isocyanate or amino resin or free radical thermal curing agent 40-45 parts

Thinner 0.4～9 parts

Cationic photoinitiator 0.1 to 3 parts

Photosensitizers and additives 0.2 to 3 parts

The curing process is: UV curing first, then microwave curing, and then UV curing; or microwave curing first, then UV curing, and then heating or microwave curing;

⑦ Cationic UV curing-anaerobic curing system, the raw materials include the following components by weight:

Epoxy resin or modified epoxy resin 60-65 parts

Dimethacrylate polyol ester or bisphenol A epoxy polyol ester 25-30 parts

Thinner 0.4～9 parts

Cationic photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 3 parts

The curing process is: firstly carry out ultraviolet light curing, then the adhesive part which is not exposed to light and under anoxic conditions will automatically undergo anaerobic curing reaction, and then carry out ultraviolet light curing;

⑧ Cationic UV curing-electron beam curing system, the raw materials include the following components by weight:

Epoxy resin or modified epoxy resin 30-35 parts

Bisphenol A vinyl ester resin, etc. 50-55 parts

Thinner 0.4～6 parts

Cationic photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 3 parts

The curing process is: first UV curing, then electron beam curing under vacuum, and then UV curing.

According to the light-emitting diode provided by the present invention, it is characterized in that the free radical thermal curing agent includes: ethylenediamine, hexamethylenediamine, triethylenetetramine, hydroxyethyldiethylenetriamine, hydroxyisopropyldiethylenetriamine Amine, polyoxalate adipamide, dimethylaminopropylamine, tetramethylpropylenediamine, dicyandiamide, diaminodiphenylsulfone, diaminodiphenylmethane, m-phenylenediamine, diethyl Toluenediamine, N-(aminopropyl)-toluenediamine, dimethylethanolamine, dimethylbenzylamine, triethylbenzylamine chloride, benzyl-dimethylamine, N-benzyldimethylamine , 2,4,6,-three-(dimethylaminomethyl)-phenol, hexamethylenediamine phenol formaldehyde, N,N-dimethylbenzylamine, 2-ethylimidazole, 2-phenylimidazole, 2 -Methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-aminoethyl)-2-methylimidazole, maleic anhydride, diphenyl ether tetraacid di Anhydride, phthalic anhydride, trimellitic anhydride, tetrabromophthalic anhydride, polynonacetic anhydride, sebacic acid dihydrazide, adipic dihydrazide, carbonate dihydrazide, oxalic acid dihydrazide, succinic acid Dihydrazide, adipic acid dihydrazide, N-amino polyacrylamide, sebacic acid hydrazide, isophthalic acid hydrazide, p-hydroxybenzoic acid hydrazide, azelaic acid dihydrazide, isophthalic acid dihydrazide Hydrazide, ferrocenetetrafluoroborate, triallyl cyanurate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, benzene Dimethylene diisocyanate, tetramethylxylylene diisocyanate, methyl styrene isocyanate, hexahydrotoluene diisocyanate, triphenylmethane-4,4',4'-triisocyanate, diaminodiphenyl Methyl urea, N-p-chlorophenyl-N-N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-p-chlorophenyl-1,1-dimethylurea, 4, 4'-Diaminodiphenylbisphenol, polyurethane, urea-formaldehyde resin, epoxy-ethylenediamine carbamate, 2,4,6-tris(dimethylaminomethyl)phenol, 2,4 -Diaminotoluene, polyurethane, methyl etherified urea-formaldehyde resin, tris(3-aminopropyl)amine, 2-aminoethyl-bis(3-aminopropyl)amine, 4,4'-diaminodi Benzyl methane, 4,4'-diaminodiphenylbisphenol, 4,4'-diaminodiphenylsulfone, tris(3-aminopropyl)amine, melamine resin, benzomelamine resin, hexamethylolmelamine Resin, hexamethoxymethyl melamine resin, urea-melamine formaldehyde resin, polyester melamine, trichloroisocyanurate, aminotriazine resin, urethane acrylate, 4-aminopyridine resin, N-β-ammonia Ethyl amino polyester resin, α-aminopyridine resin, amino diphenyl ether resin, amino phosphoric acid resin, hydroxyethyl amino polyester resin; the microwave curing adhesive and thermal curing adhesive use the same material or different materials; the anaerobic Curing adhesives include: Tetraethylene glycol dimethacrylate, Polyethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, Ethylene glycol dimethacrylate, Methacrylic acid Hydroxyethyl or Hydroxypropyl Ester, Methoxylated Polyethylene Glycol Methacrylic Ester, triethylene glycol phthalate, β-hydroxyethyl methacrylate, triethylene glycol dimethacrylate, thiodiethylene glycol dimethacrylate, phthalic acid Bis(diethylene glycol acrylate), ethoxylated bisphenol A dimethacrylate, bisphenol A glycol dimethacrylate, ethylene glycol methacrylate, triethylene glycol dimethyl Acrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, epoxy methacrylate, diethylene glycol dimethacrylate Alcohol ester; The electron beam curing adhesive includes: triphenolyl methane glycidyl ether epoxy resin, dicyclopentadiene bisphenol type epoxy resin, bisphenol A type vinyl ester resin, epoxy vinyl ester resin, Epoxy acrylate resin, maleimide resin, 4,4'-diphenylmethane bismaleimide, bisphenol A-diphenyl ether bismaleimide, bisphenol A maleic acid Vinyl resin, brominated vinyl ester resin, novolac epoxy vinyl ester resin, methylolated bisphenol A epoxy resin, bisphenol A acrylate, urethane acrylate, bisphenol A epoxy vinyl ester resin , Bisphenol A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, bisphenol A type epoxy acrylate resin, bisphenol A diglycidyl ether or bisphenol A epoxy chloroacrylate resin.

According to the light-emitting diode provided by the present invention, it is characterized in that the photoinitiator includes benzoin and its derivatives benzoin methyl ether, benzoin ether, acetophenone derivatives or benzoin isopropyl ether, and the cationic photoinitiator includes aromatic sulfonium Salt, iodonium salt or ferrocene salt, photosensitizer includes benzophenone, thioxanthraquinone or Michler's ketone, and auxiliary agent includes plasticizer, thixotropic agent or filler.

According to the light-emitting diode provided by the present invention, it is characterized in that the plasticizer includes: dioctyl phthalate, dibutyl phthalate, tributoxy vinyl phosphate, polyvinyl butyral Aldehyde, Acetyl tributyl citrate, Dimethyl phthalate, Diethyl phthalate, Bis(butoxyethoxy)ethyl adipate, Isopropyl titanate, n-Butyl titanate ester, citrate, (2-ethyl)hexyl trimellitate, di(2-ethyl)hexyl phthalate, di(2-ethyl)hexyl sebacate, diethyl Glycol dibenzoate, phthalic anhydride, dipropylene glycol dibenzoate, and chlorosulfonated polyethylene; the coupling agents include methylvinyldichlorosilane, methylhydrogendichlorosilane, Methyldichlorosilane, dimethylmonochlorosilane, vinyltrichlorosilane, γ-aminopropyltrimethoxysilane, polydimethylsiloxane, polyhydrogenmethylsiloxane, polymethylmethoxy γ-propyl methacrylate trimethoxysilane, γ-aminopropyl triethoxysilane, γ-glycidyl ether propyl trimethoxysilane, aminopropyl silsesquioxane, γ-Methacryloxypropyltrimethoxysilane, Long-chain Alkyltrimethoxysilane, Vinyltriethoxysilane, Vinyltrimethoxysilane, γ-Chloropropyltriethoxysilane, Bis-(γ-triethoxysilylpropyl), anilinomethyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl base)-γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(2,3-glycidoxy)propyl Trimethoxysilane, γ-(methacryloxy)propyltrimethylsilane, γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane.

According to the light emitting diode provided by the present invention, it is characterized in that the LED chip is a chip emitting blue light or ultraviolet light; the fluorescent powder is a fluorescent material that is excited by a blue light or ultraviolet light to emit light.

A method for preparing a light-emitting diode, comprising the following steps:

①Select the LED chip that matches the phosphor, so that the light emitted by the LED chip can effectively excite the phosphor;

②Choose a suitable die-bonding adhesive to bond the LED chip on the bracket or heat sink. When there is an electrode on the top and bottom of the LED chip, the die-bonding adhesive is required to conduct electricity and heat; when there are two electrodes on the top of the LED chip When an electrode is used, it is required that the die-bonding glue can both insulate and conduct heat;

③ Lead out the electrodes on the LED chip;

④The LED chip is coated with a light-emitting layer material. The light-emitting layer is a mixed system of phosphor powder and an adhesive that requires double curing. The double curing is completed through two independent curing stages, one of which is through ultraviolet light curing reaction , the other stage is a dark reaction, and the adhesives requiring dual curing include UV curing-thermal curing system, UV curing-microwave curing system, UV curing-anaerobic curing system and UV curing-electron beam curing system;

5. Carry out ultraviolet light curing treatment to the luminescent layer obtained in step 4. for 30 seconds;

⑥The luminescent layer obtained in step ④ is thermally cured or put into a microwave oven for microwave curing;

⑦Use ultraviolet light again to irradiate the luminescent layer for photocuring;

8. Encapsulating the light-emitting diode prepared above;

⑨Test the photoelectric properties and parameters of the device.

When using a UV curing-heat curing or UV curing-microwave curing system, the order used is to first heat or microwave curing, then UV curing, then heat curing or microwave curing; or UV curing first , and then heat curing or microwave curing, and then UV curing.

According to the preparation method of the light-emitting diode provided by the present invention, it is characterized in that in step ④, the material of the light-emitting layer is directly prepared on the LED chip after being mixed evenly, or is prepared on the LED chip after being diluted with an organic solvent; the light-emitting layer is It is formed by one or several methods of drop coating, spin coating, dip coating, coating, inkjet printing, roller coating, and LB film.

The technical solution of the present invention proposes for the first time a mixed system composed of one or more fluorescent powders capable of emitting various colors of light and an adhesive that requires double curing. By adjusting the proportion of the adhesive components that require dual curing, the obtained The colloid with appropriate viscosity enables the phosphor to be uniformly dispersed in the colloid, improves the uniformity of the glue, and solves the problem of phosphor precipitation in the colloid, which not only increases the consistency of the phosphor coating during the dispensing process , improve the consistency of the light output of the LED, and at the same time because the fluorescent powder is uniformly dispersed in the colloid, the luminous efficiency of the LED is increased; because the adhesive in the light-emitting layer of the present invention is double-cured, it solves the problem of colloid in the dispensing process. The problem of solidification, so there is no need to maintain a certain temperature and constant stirring for the equipment used in the dispensing of fluorescent powder, the container for the glue, etc. during the dispensing process, which reduces the production cost; combine light curing with other curing methods In order to make up for the shortcomings of the UV curing system, this new curing method combines the advantages of various polymerization reactions and shows a good synergistic effect. It is a new method for polymer material modification and expands the UV curing system between opaque media , substrates with complex shapes, ultra-thick coatings and colored coatings, etc.

Description of drawings

Fig. 1 is a schematic diagram of the structure of a light emitting diode provided by the present invention;

Fig. 2 is the structural representation of embodiment 1～4 provided by the present invention;

Fig. 3 is the structural representation of embodiment 5～10 provided by the present invention;

Fig. 4 is a comparison chart of luminous performance of two kinds of LEDs, wherein device A is the LED in Example 10 of the present invention, and device B is the LED in which the adhesive of the light-emitting layer adopts conventional colloid.

Among them, 1. bracket, 2. crystal-bonding glue, 3. LED chip, 4. gold wire, 5. light-emitting layer, 6. outer packaging glue.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

The technical solution of the present invention is to provide a light-emitting diode. As shown in Figure 2, the structure of the device includes a bracket 1, a crystal-bonding glue 2, an LED chip 3, a gold wire 4, a light-emitting layer 5, and an outer packaging glue 6, wherein the LED chip 3 is located on the surface of the bracket 1, and the luminescent layer 5 is located on the surface of the LED chip 3.

As shown in Figure 3, the structure of the device includes a bracket 1, a crystal-bonding glue 2, an LED chip 3, a gold wire 4, a light-emitting layer 5, and an outer packaging glue 6, wherein the LED chip 3 is located on the surface of the bracket 1, and the light-emitting layer 5 is located on the LED chip. 3 surfaces.

In the present invention, the support 1 is the support of the light-emitting diode, which requires good chemical stability and thermal stability, good electrical conductivity and thermal conductivity.

Among the present invention, the crystal-bonding glue 2 is used to bond the LED chip 3 to the support. When there is an electrode on the top and the bottom of the LED chip, it is required that the crystal-bonding glue can conduct electricity and heat conduction; when there are two electrodes on the LED chip, When an electrode is used, it is required that the die-bonding glue can both insulate and conduct heat.

In the present invention, the LED chip 3 is used as a light source to excite the fluorescent powder to emit light, which requires a good optical power and a good match between the light emitting wavelength and the fluorescent material, and a blue light or ultraviolet light chip is usually used.

In the present invention, the material of the light-emitting layer 5 is a mixed system composed of one or more fluorescent powders capable of emitting light of various colors and an adhesive that requires double curing. The double curing is completed through two independent curing stages, one of which is The first stage is through UV curing reaction, and the other stage is dark reaction. The adhesives that require dual curing include UV curing-thermal curing system, UV curing-microwave curing system, UV curing-anaerobic curing system and UV curing Curing - electron beam curing system:

① Radical UV curing-thermal curing system, the raw materials include the following components by weight:

Unsaturated polyester resin or acrylic resin or polythiol-polyene 30-40 parts

Epoxy resin or isocyanate or amino resin or free radical thermal curing agent 45 parts

Styrene and its derivatives or monofunctional or multifunctional acrylic acid 0.2 to 3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

The curing process is: UV curing first, then heating and curing, and then UV curing; or heating and curing first, then UV curing, and then heating and curing;

② Radical UV curing-microwave curing system, the raw materials include the following components by weight:

Unsaturated polyester resin or acrylic resin or polythiol-polyene 30-40 parts

Epoxy resin or isocyanate or amino resin or free radical thermal curing agent 35-45 parts

Styrene and its derivatives or monofunctional or multifunctional acrylic acid 0.2 to 3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

The curing process is: UV curing first, then microwave curing, and then UV curing; or microwave curing first, then UV curing, and then heating or microwave curing;

③ Radical UV curing-anaerobic curing system, the raw materials include the following components by weight:

Unsaturated polyester resin or acrylic resin or polythiol-polyene 55-65 parts

Dimethacrylate polyol ester or bisphenol A epoxy polyol ester 20-30 parts

Styrene and its derivatives or monofunctional or multifunctional acrylic acid 0.2 to 3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

The curing process is: firstly, UV curing is carried out, and then the part of the adhesive that is not exposed to light and under anoxic conditions will automatically undergo anaerobic curing reaction, and then UV curing;

④ Radical UV curing-electron beam curing system, the raw materials include the following components by weight:

Unsaturated polyester resin or acrylic resin or polythiol-polyene 35-40 parts

Bisphenol A vinyl ester resin, etc. 50-55 parts

Styrene and its derivatives or monofunctional or multifunctional acrylic acid 0.2 to 3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

The curing process is: first UV curing, then electron beam curing under vacuum, and then UV curing;

⑤ Cationic UV curing-heat curing system, raw materials include the following components by weight:

Epoxy resin or modified epoxy resin 35-45 parts

Epoxy resin or isocyanate or amino resin or free radical thermal curing agent 40-45 parts

Thinner 0.4～9 parts

Cationic photoinitiator 0.1 to 3 parts

Photosensitizers and additives 0.2 to 3 parts

The curing process is: UV curing first, then heating and curing, and then UV curing; or heating and curing first, then UV curing, and then heating and curing;

⑥ Cationic UV curing-microwave curing system, the raw materials include the following components by weight:

Epoxy resin or modified epoxy resin 35-45 parts

Epoxy resin or isocyanate or amino resin or free radical thermal curing agent 40-45 parts

Thinner 0.4～9 parts

Cationic photoinitiator 0.1 to 3 parts

Photosensitizers and additives 0.2 to 3 parts

The curing process is: UV curing first, then microwave curing, and then UV curing; or microwave curing first, then UV curing, and then heating or microwave curing;

⑦ Cationic UV curing-anaerobic curing system, the raw materials include the following components by weight:

Epoxy resin or modified epoxy resin 60-65 parts

Dimethacrylate polyol ester or bisphenol A epoxy polyol ester 25-30 parts

Thinner 0.4～9 parts

Cationic photoinitiator 0.1 to 3 parts

Photosensitizers and additives 0.2 to 3 parts

The curing process is: firstly carry out ultraviolet light curing, then the adhesive part which is not exposed to light and under anoxic conditions will automatically undergo anaerobic curing reaction, and then carry out ultraviolet light curing;

⑧ Cationic UV curing-electron beam curing system, the raw materials include the following components by weight:

Epoxy resin or modified epoxy resin 30-35 parts

Bisphenol A vinyl ester resin, etc. 50-55 parts

Thinner 0.4～6 parts

Cationic photoinitiator 0.1~3 parts

Photosensitizer and additives 0.2～3 parts

The curing process is: first UV curing, then electron beam curing under vacuum, and then UV curing.

In the present invention, each component of the adhesive that needs dual curing adhesive is described as follows:

Due to the use of ultraviolet light as the curing energy source, UV curing technology has its own limitations, which are mainly manifested in: there are certain restrictions on the shape of the applied substrate, the curing speed of the colored system is low, and the deep layer and the shadow area of the object It is difficult to cure, and the large volume shrinkage after curing causes problems such as poor adhesion and photoinitiator residue. These deficiencies have affected the further development and application of UV curing technology, and the disadvantage of large volume shrinkage after curing has also seriously affected the application range of UV curing materials. Dual-curing technology is a combination of light curing and other curing methods.

In the dual curing system, the crosslinking or polymerization reaction of the system is completed through two independent stages with different reaction principles, one of which is through the light curing reaction, while the other is through the dark reaction. Among them, the light curing can be free radical UV curing or cationic UV curing; the dark curing can be thermal curing, electron beam curing, anaerobic curing and microwave polymerization. In this way, light curing can be used to quickly set the system or reach surface dryness, while dark reaction can be used to completely cure the shadow part or bottom part.

Both light curing and dark curing stages can be aimed at free radical and cationic UV curing adhesives, so there are free radical and cationic thermal curing.

Below are some typical systems and some specific operating parameters.

Free radical UV curing agents include: polyester-acrylate, epoxy-acrylate, urethane

Cationic UV curing agents include: epoxy resin or modified epoxy resin.

Plasticizers include dioctyl phthalate, dibutyl phthalate, tributoxyvinyl phosphate, polyvinyl butyral, acetyl tributyl citrate, dimethyl phthalate , diethyl phthalate, bis(butoxyethoxy) ethyl adipate, isopropyl titanate, n-butyl titanate, citrate, trimellitic acid (2-ethyl) Hexyl ester, Di(2-ethyl)hexyl phthalate, Di(2-ethyl)hexyl sebacate, Diethylene glycol dibenzoate, Phthalic anhydride, Dipropylene glycol Dibenzoate and chlorosulfonated polyethylene; the coupling agents include methylvinyldichlorosilane, methylhydrogendichlorosilane, dimethyldichlorosilane, dimethylmonochlorosilane, vinyltrichlorosilane, Chlorosilane, γ-Aminopropyltrimethoxysilane, Dimethicone, Polyhydromethylsiloxane, Polymethylmethoxysiloxane, γ-Propyltrimethoxymethacrylate Silane, γ-aminopropyltriethoxysilane, γ-glycidyl ether propyltrimethoxysilane, aminopropyl silsesquioxane, γ-methacryloxypropyltrimethoxysilane, long Alkyltrimethoxysilane, Vinyltriethoxysilane, Vinyltrimethoxysilane, γ-Chloropropyltriethoxysilane, Bis-(γ-triethoxysilylpropyl), Aniline Methyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, N- β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(2,3-glycidoxy)propyltrimethoxysilane, γ-(methacryloyloxy)propyl Trimethylsilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane.

Free radical active diluents are divided into the first-generation acrylic multifunctional monomers developed earlier, the second-generation acrylic multifunctional monomers developed recently, and the more excellent third-generation acrylic monomers.

Monofunctional reactive diluents are: styrene, N-vinylpyrrolidone, isooctyl acrylate, hydroxyethyl acrylate and isobornyl acrylate, methacrylate phosphate and isobornyl methacrylate, the latter two being good plasticizing and toughening monomer.

Difunctional reactive diluents are: triethylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, and propoxyneopentyl Diol diacrylate, acrylate functional monomers mainly include 1,6-hexanediol diacrylate (HDDA), 1,4-butanediol diacrylate (BDDA), propylene glycol diacrylate (DPGDA), propane Triol Diacrylate (TPGDA), Trifunctional Trimethylolpropane Triacrylate (TMPTA), Pentaerythritol Triacrylate (PETA), Trihydroxymethylpropane Triol Triacrylate (TMPTMA), Trimethylolpropane Triacrylate Propane Triacrylate, Propoxylated Trihydroxymethylpropane Triacrylate, Pentaerythritol Tripropenol, Propoxylated Pentaerythritol Propyl Ester, Methyl N,N-Dihydroxyethyl-3-Aminopropionate , triethylene glycol dimethacrylate, long-chain aliphatic hydrocarbon glycidyl ether acrylic acid, resorcinol diglycidyl ether, dipentaerythritol pentaacrylate, tripropylene glycol diacrylate, phthalate di Diethyl alcohol diacrylate (PDDA). They replace less reactive first-generation acrylic monofunctional monomers. However, with the rapid development of UV curing technology, their shortcomings of great irritation to the skin have emerged.

The second-generation acrylic polyfunctional monomer mainly introduces ethoxy or propoxy groups into the molecule, which overcomes the disadvantage of high irritation, and should also have higher activity and curing degree. Such as ethoxylated trimethylolpropane triol triacrylate (TMP(EO)TMA), propoxylated trimethylolpropane triol triacrylate (TMP(PO)TMA), propoxylated propane Triol Triacrylate (G(PO)TA). The third-generation acrylic monomer is mainly methoxy-containing acrylate, which better solves the contradiction between high curing speed, shrinkage rate and low curing degree. Such materials include 1,6-hexanediol methoxy monoacrylate (HDOMEMA), ethoxylated neopentyl glycol methoxy monoacrylate (TMP(PO)MEDA). After the alkoxy group is introduced into the molecule, the viscosity of the monomer can be reduced, and the irritation of the monomer can be reduced at the same time.

The introduction of alkoxy groups also greatly improves the compatibility of diluent monomers. Vinyltriethoxysilane (A15I) and γ-methacryloxypropyltrimethoxysilane (A174) can be used as monomers .

Various active epoxy resin diluents and various cyclic ethers, cyclic lactones, vinyl ether monomers, etc. can be used as diluents for cationic photocurable resins. Among them, vinyl ether compounds and oligomers have fast curing speed, moderate viscosity, odorless and non-toxic, and can be used in conjunction with epoxy resin. Vinyl ether monomers include: 1,2,3-propanetriol glycidyl ether (EPON-812), triethylene glycol divinyl ether (DVE-3), 1,4-butanediol vinyl ether ( HBVE), cyclohexyl vinyl ether (CHVE), perfluoromethyl vinyl ether (PMVE), perfluoro-n-propyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether, vinyl ethyl ether, Ethyl vinyl ether, ethyl vinyl ether propylene, ethylene glycol monoallyl ether, hydroxybutyl vinyl ether, butyl vinyl ether, chlorotrifluoroethylene (CTFE), triethylene glycol divinyl ether , vinyl methyl ether, vinyl n-butyl ether, dodecyl vinyl ether (DDVE), cyclohexyl vinyl ether, tribenzylphenol polyoxyethylene ether, tetrafluoroethylene-perfluoropropyl vinyl ether , tetrafluoroethylene-perfluoropropyl vinyl ether, tert-butyl vinyl ether:

Epoxy compound monomers include: 3,4-epoxycyclohexylcarboxylic acid-3′,4′-epoxycyclohexylmethyl ester (ERL-4221), bisphenol A epoxy resin (EP), epoxy Acrylates, epoxy vinyl esters, epoxy acrylates, epoxy methacrylates, water soluble epoxy itaconate resins:

The function of the photoinitiator is to generate free radicals through decomposition after absorbing ultraviolet light energy, thereby initiating the polymerization of unsaturated bonds in the system, and crosslinking and curing into a whole. Commonly used free radical photoinitiators include cracking type and hydrogen extraction type.

Cleavage-type photoinitiators: Cleavage-type photoinitiators mainly include benzoin ethers (benzoin ethers), benzil ketals, and acetophenones. The cleavage-type photoinitiator cracks after absorbing ultraviolet light, generating two free radicals, which initiate the polymerization of unsaturated groups. Benzoin ethers (benzoin ethers) include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin oxime, benzoin isopropyl ether; Acylphosphine oxides include: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO) and (2,4,6-trimethylbenzoyl)phenylphosphine oxide (BAPO phenylbis(2, 4,6-trimethylbenzoyl)phosphine oxide), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), tetramethylpiperidone oxide (TMPO), triethyl phosphate (TEPO), they are ideal photoinitiators, have high photoinitiation activity, absorb long-wave near ultraviolet rays, are suitable for white coatings and thick films, and have good stability and will not change color or faded.

Hydrogen-extracting initiators: Hydrogen-extracting initiators mainly include benzophenones and thioxanthones. Among them, the thioxanthone photoinitiator has a maximum absorption wavelength of 380-420nm in the near-ultraviolet region, has strong absorption capacity and hydrogen abstraction capacity, and has high initiation efficiency. The hydrogen-extracting initiator must have a hydrogen donor as a synergistic component, otherwise, the initiation efficiency is too low to be put into practice. The triplet carbonyl radical is more likely to extract hydrogen from the tertiary carbon of the hydrogen donor molecule than the secondary carbon or methyl group, and the hydrogen attached to heteroatoms such as oxygen or nitrogen is easier to extract than the hydrogen on carbon atoms. Such hydrogen donors include amines, alcohol amines (triethanolamine, methyldiethanolamine, triisopropanolamine, etc.), mercaptans, and N,N-diethyl-p-dimethylaminobenzamide.

Benzophenone photoinitiation system, benzophenone needs to be used in combination with alcohol, ether or amine to make vinyl monomers photopolymerize. Mainly include: benzophenone, thioxanthraquinone, Michler's ketone, dimethoxybenzyl phenyl ketone (DMPA), α-hydroxy-2,2 dimethylacetophenone (1173), α- Hydroxycyclohexylphenylketone (184), α-aminoalkylphenone, 2-methyl-1(4-methylmercaptophenyl)-2-morpholinoacetone (MMMP), 2,2'-di Benzamidodiphenyl disulfide (DBMD), (4-dimethylaminophenyl)-(1-piperidinyl)-methanone, isopropylthioxanthone (ITX), (4-di Methylaminophenyl)-(4-morpholino)-methanone, 2-hydroxy-2-methyl-1-phenyl-1-phenyl-1-propanone, diphenoxybenzophenone, hydroxy- 2-Methylphenylpropan-1-one. And mixed systems, such as the coordinated initiator system of benzophenone and tertiary ammonia that can eliminate the inhibition of oxygen in the film to free radical polymerization; Michler's ketone and benzophenone are used in conjunction to obtain cheaper and very effective initiator system.

Cationic photoinitiator: Aromatic sulfonium salt and iodonium salt initiators have excellent high temperature stability and are also stable when combined with epoxy resin, so they are widely used in cationic curing systems. Such initiators include: xylyl iodide hexafluorophosphate (PI810), hydroxyphenyl iodonium salt (HTIB), 4,4-didodecylphenyliodonium hexafluoroantimonate, xylyl iodide Onium salt, iodonium diphenylhexafluoroarsenate, [4-(2-hydroxy-3-butoxy-1-propoxy)phenyl]phenyliodonium-hexafluoroantimonate, [4- (p-benzoylphenylthio)phenyl]phenyliodonium hexafluorophosphate, [4-(4-benzoylphenoxy)phenyl]phenyliodonium hexafluorophosphate, 4-(p-benzoylphenoxy Acylphenylthio)phenyl]phenyliodonium hexafluorophosphate, 4,4′-dimethyldiphenyliodonium hexafluorophosphate (IHT-PI 820), 4,4′-diacetamido Diphenyliodohexafluorophosphate, 37-dinitrodibenzocyclic iodonium salt and 3,7-dinitrodibenzocyclic bromide salt, tetrafluoroborate diaryliodonium salt, 3 , 3′-dinitrodiphenyliodonium salt, 3,3′-dinitrodiphenyliodonium salt and several 2,2′-disubstituted (iodo, bromo, chloro)-5,5′ -Dinitrophenyliodonium salt, 2-[2-(3-indolizine)vinyl]-1-methylquinolinium iodide, 4-(2-benzoxazole) iodide- N-methylpyridinium salt, 3-nitrophenyldiphenylthiohexafluorophosphate, triarylphosphine dihydroimidazolium salt, triarylphosphine 1,1'-binaphthyl dihydroimidazolium salt, 3 , 7-Dinitrodibenzobromopentacyclic salt, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium bromide, (4-phenylthio-phenyl) diphenylsulfide Onium hexafluorophosphate, 4-(phenylthio)triphenylsulfonium hexafluorophosphate, 3,3'-dinitrodiphenyliodohexafluorophosphate, 3-nitrophenyldiphenylsulfur Hexafluorophosphate, triphenylsulfonium salt, 4-chlorophenyldiphenylthiohexafluorophosphate, 3-nitrophenyldiphenylthiohexafluorophosphate, 4-acetamidophenyldiphenyl Triphenylthiohexafluorophosphate, 3-benzoylphenyldiphenylthiohexafluorophosphate, triphenylthiofluoroborate, triphenylthiohexafluorophosphate, triphenylthiohexafluoroantimonate , 4-tolyldiphenylthiohexafluorophosphate, phosphorus hexafluoride triarylsulfonium salt, antimony hexafluoride triarylsulfonium salt, [4-(p-benzoylphenylthio)phenyl]phenyl Ionium hexafluorophosphate, 1-(4'-bromo-2'-fluorobenzyl)pyridinium salt, [4-(p-benzoylphenylthio)phenyl]phenyliodonium hexafluorophosphate, { 4-[4-(p-Nitrobenzoyl)phenylthio]phenyl}phenyliodonium hexafluorophosphate, {4-[4-(p-methylbenzoyl)phenylthio]phenyl}phenyl Ionium hexafluorophosphate, {4-[4-(p-methylbenzoyl)phenoxy]phenyl}phenyliodonium hexafluorophosphate, [4-(p-benzoylphenoxy)benzene] Phenyliodonium hexafluorophosphate, 4,4-didodecylphenyliodonium hexafluoroantimonate.

Ferrocene salts: The photoinitiating system of ferrocene salts is a new cationic photoinitiator developed after diaromatic iodonium salts and triaromatic sulfonium salts, mainly including: cyclopentadienyl-iron-benzene salt, Cyclopentadienyl-iron-toluene salt, cyclopentadienyl-iron-p-xylene salt, cyclopentadienyl-iron-naphthalene salt, cyclopentadienyl-iron-biphenyl salt, cyclopentadienyl Alkenyl-iron-2,4-dimethylacetophenone salt, acetyl-cyclopentadienyl-iron-p-xylene salt, cyclopentadienyl-iron-anisole salt, cyclopentadiene Base-iron-diphenyl ether salt, cyclopentadienyl-iron-2,4-diethoxybenzene salt, ferrocene tetrafluoroborate, tolyl ferrocene tetrafluoroborate, cyclopentadiene Cyclopentadienyl-iron-anisole salt, cyclopentadienyl-iron-diphenyl ether salt, cyclopentadienyl-iron-1,4-diethoxybenzene salt, cyclopentadienyl-iron-chloro Benzene salt, cyclopentadienyl-iron-(1,4-diethoxybenzene) hexafluorophosphate, cyclopentadienyl-iron-diphenyl ether hexafluorophosphate, 1,10-o-diazepine Ferrous phenanthrene perchlorate, 1,10-phenanthrene ferrous sulfate cyclopentadienyl-iron-anisole salt, cyclopentadienyl-iron-diphenyl ether salt, [1 , 1'-bis(diphenylphosphino)ferrocene]nickel dichloride, vinyl ferrocene, N,N'-bis-ferrocenemethylene butanediamine quaternary ammonium salt, ferrocene formamide, Ferrocenylpropionic acid, acetylferrocene, ethylferrocene, butyrylferrocene, butylferrocene, N,N-dimethyl-aminomethylferrocene, 1,1' - Dibenzoylferrocene, (3-carboxypropionyl)ferrocene, 1,1'-dibromoferrocene, aminoferrocene.

UV curing-heat curing system: It is found that the mechanical properties of the cured product after heat treatment have been significantly improved, and with the increase of epoxy components, the hybrid system has good adhesion on metal and other substrates. On the one hand, it is due to the small shrinkage of the epoxy compound during curing, and on the other hand, due to the elimination of the internal stress generated during the free radical photocuring during thermal curing. According to the substrate for flexible optoelectronic devices provided by the present invention, it is characterized in that the thermal curing agent in the thermal curing method includes: epoxy resins, isocyanates, amino resins and free radical thermal curing agents.

Epoxy resins include: aliphatic amines, aromatic amines, dicyandiamide, imidazoles, organic acid anhydrides, organic hydrazides, Lewis acid amines and microcapsules.

Aliphatic amines include: ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hydroxyethyldiethylenetriamine, hydroxyisopropyldiethylenetriamine, polyoxalic acid adipamide, Ethanolamine, tetramethylethylenediamine, diamine glycyrrhizinate, N-(2-hydroxyethyl)ethylenediamine, bis(4-aminophenoxy)-phenylphosphine oxide, bis(3-aminophenyl base) phenylphosphine oxide, tetrapropylene glycol diamine, N-hydroxyethyl ethylenediamine, methylcyclopentadiamine, polyether amine, phenalkamine curing agent (T-31), hydroxyethyl ethylenediamine, Isophoronediamine, menthanediamine, dimethylaminopropylamine, bis(4-amino-3-methylcyclohexyl)methane, tetramethylpropylenediamine, modified amine epoxy curing agent (593), Aliphatic amine epoxy curing agent (3380, TG-03, LX-502, D230), fatty amine modified adduct (HB-206, HB-205, HB-2512, HB-9305, HB-9409).

Dicyandiamide includes: dicyandiamide, 3,5 disubstituted aniline modified dicyandiamide derivatives (HT 2833, HT 2844), dicyandiamide (MD 02, prepared by the reaction of propylene oxide and dicyandiamide ), modified dicyandiamide derivatives (AEHD-610, AEHD-210), and derivatives containing the following molecular formula.

Aromatic amines include: diaminodiphenylsulfone (DDS), diaminodiphenylmethane (DDM), m-phenylenediamine (m PDA), 8-m-naphthalenediamine, diethyltoluenediamine, O-phenylenediamine, p-phenylenediamine, allyl aromatic diamine, N-(aminopropyl)-toluenediamine, isophorone diamine, dimethylethanolamine, dimethylbenylamine, triethyl Benzylamine chloride, benzyl-dimethylamine, N-benzyldimethylamine, 2,4,6,-tris-(dimethylaminomethyl)-phenol, phenol formaldehyde hexamethylenediamine, N,N -Dimethylbenzylamine (BDMA), N-p-carboxyphenylmaleimide (p-CPMD).

Imidazoles include: 1-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-methylimidazole, 1-8-aminoethyl-2-methylimidazole (AMz), 2-undecane Di-imidazole adipate, 2-ethylimidazole, 2-ethyl-4-methylimidazole (2E4Mz), 1-(2-aminoethyl)-2-methylimidazole, 1-cyano-2 -Ethyl-4-methylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole-carboxyl, 3-dimethylol-substituted imidazole derivatives, 1,3-diphenyl- 2-methylimidazole chloride, 1-decyl-2-ethylimidazole, modified imidazole (JH-0511, JH-0512, JH-0521).

Organic acid anhydrides include: epoxidized polybutadiene/anhydride, maleic anhydride, 70# anhydride (synthesized from butadiene and maleic anhydride), 647# anhydride (synthesized from dicyclopentadiene and maleic anhydride) Synthesis of olefinic anhydride), 308 tungoleic anhydride (synthesized from tung oil modified maleic anhydride, methyl endomethylene tetrahydrophthalic anhydride (MNA)), pyromellitic dianhydride (PMTA) ( Pyromellitic dianhydride mixed with maleic anhydride), methyl hexahydrophthalic anhydride (MeHHPA), diphenyl ether tetracarboxylic dianhydride, phthalic anhydride (PA), hexahydrophthalic anhydride (HHPA ), tetrahydrophthalic anhydride (THPA), methyltetrahydrophthalic anhydride, epoxidized polybutadiene/anhydride, trimellitic anhydride (TMA), tetrabromophthalic anhydride, polynonacetic anhydride (PAPA).

Organic hydrazides include: sebacic acid dihydrazide (SDH), adipic dihydrazide, carbonate dihydrazide, oxalic acid dihydrazide, succinic acid dihydrazide, adipate dihydrazide, N-aminopolypropylene Amide, N(CH ₂ CH ₂ CO-NHNH ₂ ) ₃ , (H ₂ NHNCOCH ₂ CH ₂ ) ₂ NCH ₂ CH ₂ N(CHCHCONHNH ₂ ) ₂ , Succinic Hydrazide, Sebacic Hydrazide, Isophthalic Acid Hydrazide, p-hydroxybenzoic acid hydrazide (POBH), azelaic acid dihydrazide, isophthalic acid dihydrazide.

Lewis acid amines are composed of BF ₃ , AlCl ₃ , ZnCl ₂ , PF ₅ and other Lewis acids and primary or secondary amines to form complexes, including: cyclopentadienyl cumene iron hexafluorophosphate (Irgacure 261), boron trifluoride, ferrocene tetrafluoroborate.

Microcapsules include: cellulose, gelatin, polyvinyl alcohol, polyester, polysulfone.

Isocyanates include: triallyl cyanurate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (PAPI), hexamethylene diisocyanate (HDI), isofor Alone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), dicyclohexylmethane diisocyanate (HMDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate ( TMXDI), methylstyrene isocyanate (TMI), hexahydrotoluene diisocyanate (HTDI), nitrile rubber, heptaisocyanate, triphenylmethane-4,4',4'-triisocyanate, thiophosphoric acid tris(4 -isocyanatophenyl ester), tetraisocyanate, heptaisocyanate, biuret polyisocyanate, tetrahydrofuran polyether polyol-epoxy resin-isocyanate, trihydroxypolyoxypropylene polyol-isocyanate.

Amino resins include: diaminodiphenylmethane (DDM), N-p-chlorophenyl-N-N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-p-chlorophenyl- 1,1-dimethylurea, 4,4'-diaminodiphenylbisphenol, polyurethane, urea-formaldehyde resin, epoxy-ethylenediamine carbamate, N, N, N', N '-Tetrapropargyl-4,4'-diamino-diphenylmethane (TPDDM), 2,4,6-tris(dimethylaminomethyl)phenol, 2,4-diaminotoluene, 4,6- Tris(dimethylaminomethyl)phenol, polyurethane, methyl etherified urea-formaldehyde resin, tris(3-aminopropyl)amine, 2-aminoethyl-bis(3-aminopropyl)amine, N,N , N', N'-tetrakis(3-aminopropyl)ethylenediamine, 1-[bis(3-aminopropyl)amino]-2-propanol; N-(2-aminoethyl)-N- (3-aminopropyl)amine, 1-[(2-aminoethyl)-(3-aminopropyl)amino]-1-ethanol, 1-[(2-aminoethyl)-(3-aminopropyl base)amino]-2-propanol, 3-dimethylaminopropylamine, 4,4'-aminodiphenylmethane (DDM), 4,4'-diaminodiphenylbisphenol, 4,4'-diamino Diphenyl sulfone (DDS), tris(3-aminopropyl)amine, melamine resin, benzomelamine resin, hexamethylol melamine resin, methyl etherified melamine resin, methyl etherified benzomelamine resin, methyl etherified urea Melamine polycondensation resin, hexamethoxymethyl melamine resin (TMMM), methanol modified trimethylol melamine, urea-melamine formaldehyde resin, polyester melamine, 2-sec-butylphenyl-N-methylamino acid ester, di Chloroisocyanurate, trichloroisocyanurate, aminotriazine resin, urethane acrylate, 4-aminopyridine resin, N-β-aminoethylaminopolyester resin, α-aminopyridine resin , amino diphenyl ether resin, amino polysiloxane, amino phosphoric acid resin, maleopimaric acid polyester amino resin, piperazine aminodithioformic acid chelating resin, hydroxyethyl amino polyester resin.

Free radical thermal curing agents include: dicumyl peroxide, epoxy monoacrylate, tert-butyl benzoate, polyurethane acrylate, polyurethane diol, polyester triol, bis(hexafluorophosphate), polymethyl Methyl Acrylate (PMMA), Styrene-Acrylate, Polybutadiene Hydroxyacrylate, Polyester Urethane Acrylate, Epoxy Monoacrylate, Butadiene-Methyl Methacrylate-Styrene Copolymer, butadiene-methyl methacrylate, ethylene-acrylate, polyacrylate, chlorinated polypropylene-acrylate, polymethyl methacrylate, polyethyl methacrylate, cyanoacrylate, 2 - 1,2-propylene glycol monoacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, Isooctyl methacrylate, 2-methylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl acrylate, isooctyl acrylate, vinyl acetate-acrylic acid Butyl ester, polymethyl methacrylate.

UV curing-microwave curing system: The microwave curing agent in the microwave curing method is the same as the thermal curing agent in the thermal curing method. Its technical feature is to use microwave curing to cure the thermal curing agent. Due to the unique "intramolecular" uniform heating method of microwave, the resin is cured uniformly, fast, easy to control, energy saving, and less equipment investment. be valued.

UV curing-anaerobic curing system: the anaerobic curing agent in the anaerobic curing system includes: tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate (such as Loctite 290 in the United States) And Loctite 271, Loctite 277 mixed with fumaric acid bisphenol A unsaturated polyester), triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, hydroxyethyl methacrylate Or hydroxypropyl ester (such as domestic iron anchor 302, Japan's triple bond 1030), bisphenol A epoxy ester (such as domestic Y-150, GY-340, etc. are a mixture of epoxy ester and polyethylene glycol ester) , the reaction product of methacrylate hydroxyalkylphenol and polyol (such as American Loctite 372, domestic GY-168, iron anchor 352 and BN-601), polyurethane, polyurethane isocyanate, hydroxypropyl methacrylate ester, hydroxypropyl methacrylate-polyether, hydroxybutyl urethane, urethane-acrylate, hydroxypropyl acrylate (HPA), ethylene glycol dimethacrylate, cumyl hydroperoxide, acrylic ortho Cresol Novolac Epoxy Ester, Methoxylated Polyethylene Glycol Methacrylate, Triethylene Glycol Phthalate, β-Hydroxyethyl Methacrylate, Trimethylolpropane Trimethacrylate , triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, thiodiethylene glycol dimethacrylate, bis(diethylene glycol acrylate), ethoxy Bisphenol A dimethacrylate, bisphenol A ethylene glycol dimethacrylate, ethylene glycol methacrylate, ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, a Diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, epoxy resin (meth)acrylate, diethylene glycol dimethacrylate, trimethacrylate Ethylene glycol ester, urethane acrylate, methyl a-cyanoacrylate, ethyl a-cyanoacrylate, glycidyl methacrylate, polyethylene glycol dimethacrylate, triethylene glycol dimethyl Acrylate, dicyclopentadienyl-oxy-ethyl methacrylate, dimethylaminoethyl methacrylate.

UV curing-electron beam curing system: the electron beam curing agent in the electron beam curing method includes: triphenolyl methane glycidyl ether epoxy resin, dicyclopentadiene bisphenol epoxy resin, bisphenol A vinyl Ester resin (V-411), epoxy vinyl ester resin (V-901), epoxy acrylate resin (BRT2000), maleimide resin, 4,4'-diphenylmethane bismaleimide , bisphenol A-diphenyl ether bismaleimide, bisphenol A maleic acid vinyl resin, vinyl ester resin, brominated vinyl ester resin, fumaric acid mixed vinyl ester resin, Acrylic mixed vinyl ester resins, urethane mixed vinyl ester resins, rubber mixed vinyl ester resins, novolac epoxy vinyl ester resins, isocyanate mixed epoxy acrylates, toluene diisocyanate mixed hydroxyethyl acrylates, hydroxy Methylated bisphenol type epoxy resin, bisphenol A acrylate, polyurethane acrylate, bisphenol A epoxy vinyl ester resin, bisphenol A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, bisphenol Phenol A type epoxy acrylate resin, bisphenol A diglycidyl ether, bisphenol A epoxy chloroacrylate resin.

The following are specific embodiments of the present invention:

Example 1

The device structure is shown in Figure 2, the LED chip 3 is a blue LED chip, the light-emitting layer 5 is a mixed system of fluorescent powder excited by blue light to produce yellow light and an adhesive that requires double curing, and the bracket 1 is a copper bracket with a silver-plated surface.

The preparation method is as follows:

①Choose a suitable die-bonding glue to glue the blue LED chip on the bracket;

② Lead out the electrodes on the LED chip;

③The luminescent layer material is drip-coated on the LED chip. The luminescent layer is a mixed system of yellow fluorescent powder and an adhesive that requires double curing. The adhesive raw material includes the following components:

Acrylic resin (free radical UV curing agent) 30-40 parts

Isocyanate (heat curing agent) 35～45 parts

Multifunctional acrylic acid (thinner) 0.2~3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

④ UV-curing the luminescent layer obtained in step ③ for 30 seconds;

⑤ Carrying out thermal curing treatment on the luminescent layer obtained in step ③, the temperature is 110°C;

⑥Use ultraviolet light to irradiate the luminescent layer again for photocuring;

⑦ Encapsulate the light-emitting diode prepared above;

⑧ Test the photoelectric properties and parameters of the device.

Example 2

The device structure is shown in Figure 2, the LED chip 3 is a blue LED chip, the light-emitting layer 5 is a mixed system of phosphor powder excited by blue light to generate green light and an adhesive that requires double curing, and the bracket 1 is a copper bracket with a silver-plated surface.

The preparation method is as follows:

①Choose a suitable die-bonding glue to glue the blue LED chip on the bracket;

② Lead out the electrodes on the LED chip;

③ Spraying the luminescent layer material on the LED chip, the luminescent layer is a mixed system of green fluorescent powder and an adhesive that requires double curing, and the adhesive raw material includes the following components:

Unsaturated polyester resin (free radical UV curing agent) 30-40 parts

Epoxy resin (heat curing agent) 35～45 parts

Multifunctional acrylic acid (thinner) 0.2~3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

④ UV-curing the luminescent layer obtained in step ③ for 30 seconds;

⑤ Carrying out thermal curing treatment on the luminescent layer obtained in step ③, the temperature is 110°C;

⑥Use ultraviolet light to irradiate the luminescent layer again for photocuring;

⑦ Encapsulate the light-emitting diode prepared above;

⑧ Test the photoelectric properties and parameters of the device.

Example 3

The device structure is shown in Figure 2, the LED chip 3 is a blue LED chip, the light-emitting layer 5 is a mixed system of phosphor powder excited by blue light to generate red light and an adhesive that requires double curing, and the bracket 1 is a copper bracket with a silver-plated surface.

The preparation method is as follows:

①Choose a suitable die-bonding glue to glue the blue LED chip on the bracket;

② Lead out the electrodes on the LED chip;

③ Dip-coat the luminescent layer material on the LED chip, the luminescent layer is a mixed system of red fluorescent powder and an adhesive that needs double curing, and the adhesive raw material includes the following components:

Epoxy resin (cationic UV curing agent) 35-45 parts

Amino resin (heat curing agent) 40-45 parts

Thinner (vinyl ether monomer) 4.0～9 parts

Cationic photoinitiator (aromatic iodonium salt) 1.2～3 parts

Photosensitizers and additives 0.2 to 3 parts

④ UV-curing the luminescent layer obtained in step ③ for 30 seconds;

⑤ Carrying out thermal curing treatment on the luminescent layer obtained in step ③, the temperature is 110°C;

⑥Use ultraviolet light to irradiate the luminescent layer again for photocuring;

⑦ Encapsulate the light-emitting diode prepared above;

⑧ Test the photoelectric properties and parameters of the device.

Example 4

The device structure shown in Figure 2, the LED chip 3 adopts a blue LED chip, the light-emitting layer 5 adopts a mixed system of fluorescent powder that is excited by blue light to generate red and green light and an adhesive that requires double curing, and the bracket 1 adopts a silver-plated copper surface. stand.

The preparation method is as follows:

①Choose a suitable solid crystal glue to glue the blue LED chip on the bracket;

② Lead out the electrodes on the LED chip;

③ Spin-coat the luminescent layer material on the LED chip. The luminescent layer is a mixed system of red and green phosphors and an adhesive that requires dual curing. The adhesive raw material includes the following components:

Wherein the ratio of adhesive raw material components is:

Polythiol-polyene (free radical UV curing agent) 55～65 parts

Polyester dimethacrylate (anaerobic curing agent) 20-30 parts

Monofunctional acrylic acid (thinner) 0.2~3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

④ UV-curing the luminescent layer obtained in step ③ for 30 seconds;

⑤ Carrying out thermal curing treatment on the luminescent layer obtained in step ③, the temperature is 110°C;

⑥Use ultraviolet light to irradiate the luminescent layer again for photocuring;

⑦ Encapsulate the light-emitting diode prepared above;

⑧ Test the photoelectric properties and parameters of the device.

Example 5

The device structure is shown in Figure 3. The LED chip 3 is an ultraviolet LED chip. The light-emitting layer 5 is a mixed system of fluorescent powder excited by ultraviolet light to produce blue light and an adhesive that requires double curing. The bracket 1 is a copper bracket with silver-plated surface.

The preparation method is as follows:

①Choose a suitable die-bonding glue to glue the UV LED chip on the bracket;

② Lead out the electrodes on the LED chip;

③ Spin-coat the luminescent layer material on the LED chip. The luminescent layer is a mixed system of blue phosphor powder and an adhesive that requires double curing. The adhesive raw material includes the following components:

Epoxy resin or modified epoxy resin (cationic UV curing agent) 0-35 parts

Bisphenol A vinyl ester resin, etc. (electron beam curing agent) 50-55 parts

Thinner (reactive epoxy resin) 0.4～6 parts

Cationic photoinitiator (aromatic sulfonium salt) 0.1～3 parts

Photosensitizers and additives 0.2 to 3 parts

④ UV-curing the surface of the luminescent layer obtained in step ③ for 30 seconds;

5. Carrying out electron beam curing treatment to the luminescent layer obtained in step 3.;

⑥Use ultraviolet light to irradiate the luminescent layer again for photocuring;

⑦ Encapsulate the light-emitting diode prepared above;

⑧ Test the photoelectric properties and parameters of the device.

Example 6

The device structure is shown in Figure 3, the LED chip 3 is an ultraviolet LED chip, the light-emitting layer 5 is a mixed system of fluorescent powder excited by ultraviolet light to generate green light and an adhesive that requires double curing, and the bracket 1 is a copper bracket with a silver-plated surface. .

The preparation method is as follows:

①Choose a suitable die-bonding glue to glue the UV LED chip on the bracket;

② Lead out the electrodes on the LED chip;

③ Spin-coat the luminescent layer material on the LED chip, the luminescent layer is green phosphor and requires double solidification

The mixed system of the adhesive of chemicalization, described adhesive raw material comprises following component:

Acrylic resin (free radical UV curing agent) 30-40 parts

Isocyanate (heat curing agent) 35～45 parts

Multifunctional acrylic acid (thinner) 0.2~3 parts

Photoinitiator 0.1～3 parts

Photosensitizers and additives 0.2 to 6 parts

④ UV-curing the luminescent layer obtained in step ③ for 30 seconds;

⑤ Carrying out thermal curing treatment on the luminescent layer obtained in step ③, the temperature is 110°C;

⑥Use ultraviolet light to irradiate the luminescent layer again for photocuring;

⑦ Encapsulate the light-emitting diode prepared above;

⑧ Test the photoelectric properties and parameters of the device.

Example 7

The device structure shown in Figure 3, the LED chip 3 is an ultraviolet LED chip, the light-emitting layer 5 is a mixed system of fluorescent powder excited by ultraviolet light to produce yellow light and an adhesive that requires double curing, and the bracket 2 is a copper bracket with a silver-plated surface. .

The preparation method is similar to Example 6.

Example 8

The device structure is shown in Figure 3. The LED chip 3 is an ultraviolet LED chip. The light-emitting layer 5 is a mixed system of fluorescent powder that is excited by ultraviolet light to generate red light and an adhesive that requires double curing. The bracket 1 is a copper bracket with a silver-plated surface. .

The preparation method is similar to Example 6.

Example 9

The device structure is shown in Figure 3. The LED chip 3 is an ultraviolet LED chip. The light-emitting layer 5 is a mixed system of fluorescent powder that is excited by ultraviolet light to produce blue and yellow light and an adhesive that requires double curing. The bracket 1 is made of silver-plated Copper bracket.

The preparation method is similar to Example 6.

Example 10

The device structure is shown in Figure 3. The LED chip 3 is an ultraviolet LED chip. The light-emitting layer 5 is a mixed system of fluorescent powder that is excited by ultraviolet light to produce blue, green, and red light and an adhesive that requires double curing. The bracket 1 adopts a surface Silver-plated copper bracket.

The preparation method is similar to Example 6.

Table 1 shows the various performance parameters of the light-emitting diode in which conventional colloid is used as the adhesive of the light-emitting layer and the light-emitting diode in Example 10.

The adhesive of the light-emitting layer adopts the light-emitting diode of conventional colloid The light emitting diode of embodiment 10 of the present invention Maximum luminance (cd/m ² ) 21360 30810 Color rendering index 91 96 Color coordinates (0.315, 0.324) (0.328, 0.335)

lifespan (hours) ~30000 ~36700 Color temperature (k) 7653 7835

Claims (7)

1. light-emitting diode, at least comprise support, led chip and the luminescent layer on led chip, it is characterized in that, described luminescent layer material can be sent out the fluorescent material of shades of colour light for one or more and need the mixed system of the adhesive composition of dual cure, described dual cure by two independently cure stage finish, one of them stage is to react by ultraviolet light polymerization, another stage is dark reaction, and the described adhesive of dual cure that needs comprises ultraviolet light polymerization-heat cured system, ultraviolet light polymerization-microwave curing system, ultraviolet light polymerization-anaerobic curing system and ultraviolet light polymerization-electronic beam curing system:

1. free radical type ultraviolet light polymerization-heat cured system, raw material comprises the component of following weight portion:

30～40 parts of unsaturated polyester resin or acrylic resin or polythiol-polyenoid

45 parts of epoxy resin or isocyanates or amino resins class or free radical thermal curing agents

0.2～3 part in styrene and derivative thereof or simple function group or polyfunctional group acrylic acid

0.1～3 part of light trigger

0.2～6 part of sensitising agent and auxiliary agent

Solidification process is: carry out ultraviolet light polymerization earlier, then be heating and curing, carry out ultraviolet light polymerization again; Perhaps be heating and curing earlier, then carry out ultraviolet light polymerization, be heating and curing again;

2. free radical type ultraviolet light polymerization-microwave curing system, raw material comprises the component of following weight portion:

30～40 parts of unsaturated polyester resin or acrylic resin or polythiol-polyenoid

35～45 parts of epoxy resin or isocyanates or amino resins class or free radical thermal curing agents

0.2～3 part in styrene and derivative thereof or simple function group or polyfunctional group acrylic acid

0.1～3 part of light trigger

0.2～6 part of sensitising agent and auxiliary agent

Solidification process is: carry out ultraviolet light polymerization earlier, then carry out microwave curing, carry out ultraviolet light polymerization again; Perhaps carry out microwave curing earlier, then carry out ultraviolet light polymerization, again heating or microwave curing;

3. free radical type ultraviolet light polymerization-anaerobic curing system, raw material comprises the component of following weight portion:

55～65 parts of unsaturated polyester resin or acrylic resin or polythiol-polyenoid

20～30 parts of many acetals of methacrylate ester or many acetals of bisphenol-A epoxy esters

0.2～3 part in styrene and derivative thereof or simple function group or polyfunctional group acrylic acid

0.1～3 part of light trigger

0.2～6 part of sensitising agent and auxiliary agent

Solidification process is: at first carry out ultraviolet light polymerization, then be not subjected to illumination and be in adhesive segment under the anoxia condition carrying out the anaerobic curing reaction automatically, carry out ultraviolet light polymerization again;

4. free radical type ultraviolet light polymerization-electronic beam curing system, raw material comprises the component of following weight portion:

35～40 parts of unsaturated polyester resin or acrylic resin or polythiol-polyenoid

50～55 parts of bisphenol A-type vinyl ester resins etc.

0.2～3 part in styrene and derivative thereof or simple function group or polyfunctional group acrylic acid

0.1～3 part of light trigger

0.2～6 part of sensitising agent and auxiliary agent

Solidification process is: at first carry out ultraviolet light polymerization, then carry out electronic beam curing under vacuum, carry out ultraviolet light polymerization again;

5. cation type ultraviolet photo-curing-heat cured system, raw material comprises the component of following weight portion:

35～45 parts of epoxy resin or modified epoxies

40～45 parts of epoxy resin or isocyanates or amino resins class or free radical thermal curing agents

0.4～9 part of diluent

0.1～3 part of cation light initiator

0.2～3 part of sensitising agent and auxiliary agent

Solidification process is: carry out ultraviolet light polymerization earlier, then be heating and curing, carry out ultraviolet light polymerization again; Perhaps be heating and curing earlier, then carry out ultraviolet light polymerization, be heating and curing again;

6. cation type ultraviolet photo-curing-microwave curing system, raw material comprises the component of following weight portion:

35～45 parts of epoxy resin or modified epoxies

40～45 parts of epoxy resin or isocyanates or amino resins class or free radical thermal curing agents

0.4～9 part of diluent

0.1～3 part of cation light initiator

0.2～3 part of sensitising agent and auxiliary agent

Solidification process is: carry out ultraviolet light polymerization earlier, then carry out microwave curing, carry out ultraviolet light polymerization again; Perhaps carry out microwave curing earlier, then carry out ultraviolet light polymerization, again heating or microwave curing;

7. cation type ultraviolet photo-curing-anaerobic curing system, raw material comprises the component of following weight portion:

60～65 parts of epoxy resin or modified epoxies

25～30 parts of many acetals of methacrylate ester or many acetals of bisphenol-A epoxy esters

0.4～9 part of diluent

0.1～3 part of cation light initiator

0.2～3 part of sensitising agent and auxiliary agent

Solidification process is: at first carry out ultraviolet light polymerization, then be not subjected to illumination and be in adhesive segment under the anoxia condition carrying out the anaerobic curing reaction automatically, carry out ultraviolet light polymerization again;

8. cation type ultraviolet photo-curing-electronic beam curing system, raw material comprises the component of following weight portion:

30～35 parts of epoxy resin or modified epoxies

50～55 parts of bisphenol A-type vinyl ester resins etc.

0.4～6 part of diluent

0.1～3 part of cation light initiator

0.2～3 part of sensitising agent and auxiliary agent

Solidification process is: at first carry out ultraviolet light polymerization, then carry out electronic beam curing under vacuum, carry out ultraviolet light polymerization again.

2. light-emitting diode according to claim 1, it is characterized in that, described free radical thermal curing agents comprises: ethylenediamine, hexamethylene diamine, triethylene tetramine, the ethoxy diethylenetriamine, hydroxyl isopropyl diethylenetriamine, poly-ethanedioic acid adipamide, diformazan ammonia propylamine, 4-methyl-diaminopropane, dicyandiamide, two amido diphenyl sulfones, two amido diphenyl methanes, m-phenylene diamine (MPD), diethyl toluene diamine, N-(aminopropyl)-toluenediamine, dimethylethanolamine, dimethyl Bian amine, triethyl group benzyl ammonium chloride, benzyl-dimethylamine, the N-benzyl dimethylamine, 2,4,6,-three-(dimethylamino methyl)-phenol, the phenol formaldehyde (PF) hexamethylene diamine, N, the N-dimethyl benzylamine, the 2-ethyl imidazol(e), the 2-phenylimidazole, glyoxal ethyline, the 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 1-(2-amino-ethyl)-glyoxal ethyline, maleic anhydride, the diphenyl ether tetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, the tetrabromo-benzene dicarboxylic acid anhydride, gather acetic anhydride in the ninth of the ten Heavenly Stems, sebacic dihydrazide, adipic dihydrazide, carbonic acid two hydrazides, oxalic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide, the amino polyacrylamide of N-, the decanedioic acid hydrazides, the M-phthalic acid hydrazides, to the Para Hydroxy Benzoic Acid hydrazides, azelaic acid two hydrazides, isophthalic dihydrazide, the ferrocene tetrafluoroborate, triallyl cyanurate, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, hexamethylene diisocyanate, the trimethyl hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, XDI, tetramethylxylylene diisocyanate, the methyl styrene isocyanates, the hexahydrotoluene vulcabond, triphenyl first-4,4 ', 4 '-triisocyanate, diaminodiphenyl-methane, N-is to chlorophenyl-N-N-dimethyl urea, 3-phenyl-1, the 1-dimethyl urea, 3-rubigan-1, the 1-dimethyl urea, 4,4 '-the diamino-diphenyl bis-phenol, polyurethanes, Lauxite, epoxy-ethylenediamine carbamate, 2,4,6-three (dimethylamino methyl) phenol, 2, the 4-diaminotoluene, polyurethane, the methyl-etherified Lauxite, three (3-aminopropyl) amine, 2-amino-ethyl-two (3-aminopropyl) amine, 4,4 '-MDA, 4,4 '-the diamino-diphenyl bis-phenol, 4,4 '-diamino-diphenyl sulfone, three (3-aminopropyl) amine, melmac, the benzoguanamine resin, hexamethylol melamine resin, the hexamethoxymethyl melamine resin, urea-melamine resin, the polyester melamine, the TCCA ester, aminotriazine resins, urethane acrylate, the 4-aminopyridine resin, the amino mylar of N-β-aminoethyl, the α-An Jibiding resin, aminodiphenylether resin, the phosphoramidic acid resin, the hydroxyethylamino mylar; Described microwave curing adhesive and hot setting adhesive use same material or different materials; Described anaerobic curing adhesive comprises: methacrylate tetraethylene-glycol ester, methacrylate multicondensed ethylene glycol ester, the triethylene Glycol double methyl methacrylate, the methacrylate glycol ester, hydroxyethyl methacrylate or hydroxypropyl acrylate, the methoxylated polyethylene glycol methacrylate, the phthalic acid Triethylene Glycol, Jia Jibingxisuanβ-Qiang Yizhi, the triethylene Glycol double methyl methacrylate, methacrylate sulfo-diethylene glycol (DEG) ester, phthalic acid two (diethylene glycol (DEG) acrylate), the ethoxylation bisphenol a dimethacrylate, dimethacrylate bisphenol-A ethylene glycol fat, second diester methacrylate, the triethylene-glycol dimethylacrylate, the condensed ethandiol double methyl methacrylate, glycol methacrylate, one diethyl acetal double methyl methacrylate, the epoxy resin methacrylate, methacrylate diglycol ester; Described electronic beam curing adhesive comprises: triphenol methylmethane tetraglycidel ether epoxy resin, the bicyclopentadiene bisphenol-type epoxy resin, the bisphenol A-type vinyl ester resin, epoxy vinyl ester resin, Epocryl, maleimide resin, 4,4 '-diphenyl methane dimaleimide, bisphenol-A-diphenyl ether bismaleimides, bisphenol-A maleic acid vinylite, ethylene bromide base ester resin, the phenolic aldehyde epoxy vinyl ester resin, the methylolation bisphenol A type epoxy resin, the bisphenol-A acrylate, urethane acrylate, the bisphenol-A epoxy vinyl ester resin, bisphenol A benzoxazine-epoxy resin, bisphenol fluorene epoxy resin, the bisphenol-a epoxy acrylate resin, bisphenol A diglycidyl ether or bisphenol-A epoxy chloropropene acid esters resin.

3. light-emitting diode according to claim 1, it is characterized in that, described light trigger is for comprising styrax and derivative benzoin methyl ether, benzoin ethyl ether, acetophenone derivative or benzoin isopropyl ether, cation light initiator comprises aromatic sulfonium salts, salt compounded of iodine or luxuriant molysite class, sensitising agent comprises benzophenone, thia anthraquinone or Michler's keton, and auxiliary agent comprises plasticizer, thixotropic agent or filler.

4. light-emitting diode according to claim 1, it is characterized in that described plasticizer comprises: dioctyl phthalate, dibutyl phthalate, three vinyl butyl ether base phosphates, polyvinyl butyral resin, tributyl 2-acetylcitrate, repefral, diethyl phthalate, adipic acid two (butoxy ethyoxyl) ethyl ester, isopropyl titanate, tetrabutyl titanate, citrate, the own ester of trimellitic acid (2-ethyl), the own ester of phthalic acid two (2-ethyl), the own ester of decanedioic acid two (2-ethyl), the diglycol dibenzoate, phthalic anhydride, dipropylene glycol dibenzoate and chlorosulfonated polyethylene; Described coupling agent comprises the methyl ethylene dichlorosilane, methyl hydrogen dichlorosilane, dimethyldichlorosilane, chlorodimethyl silane, vinyl trichlorosilane, γ-An Bingjisanjiayangjiguiwan, dimethyl silicone polymer, poly-hydrogen methylsiloxane, poly-methyl methoxy radical siloxane, γ-methacrylic acid third vinegar base trimethoxy silane, gamma-aminopropyl-triethoxy-silane, γ-glycidol ether propyl trimethoxy silicane, the aminopropyl silsesquioxane, γ-methacryloxypropyl trimethoxy silane, the chain alkyl trimethoxy silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-chloropropyl triethoxysilane, two-(the silica-based propyl group of γ-triethoxy), anilinomethyl triethoxysilane, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane, N-β (aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) oxypropyl trimethyl silane, γ-Qiu Jibingjisanjiayangjiguiwan or γ-sulfydryl propyl-triethoxysilicane.

5. light-emitting diode according to claim 1 is characterized in that, described led chip is the chip of blue light-emitting or ultraviolet light; Described fluorescent material is by a kind of blue light or ultraviolet excitation and luminous fluorescent material.

6. the preparation method of a light-emitting diode may further comprise the steps:

1. select the led chip with the fluorescent material coupling, the effective excitated fluorescent powder of the luminous energy that led chip is sent;

2. select suitable crystal-bonding adhesive that led chip is bonded on the support, when respectively there is an electrode above and below of led chip, require crystal-bonding adhesive to conduct electricity and can heat conduction; When two electrodes are arranged above the led chip, require crystal-bonding adhesive to insulate and can heat conduction;

3. extraction electrode on led chip;

4. apply the luminescent layer material on the led chip, described luminescent layer is fluorescent material and the mixed system that needs the adhesive of dual cure, described dual cure by two independently cure stage finish, one of them stage is to react by ultraviolet light polymerization, another stage is dark reaction, the described adhesive of dual cure that needs comprises ultraviolet light polymerization-heat cured system, ultraviolet light polymerization-microwave curing system, ultraviolet light polymerization-anaerobic curing system and ultraviolet light polymerization-electronic beam curing system, when using ultraviolet light polymerization-hot curing or ultraviolet light polymerization-microwave curing system, the order that adopts is to be heating and curing earlier or microwave curing, carry out ultraviolet light polymerization then, be heating and curing again or microwave curing; Perhaps carry out ultraviolet light polymerization earlier, be heating and curing then or microwave curing, carry out ultraviolet light polymerization again;

5. the luminescent layer that 4. step is obtained carries out ultraviolet light polymerization processing 30 seconds;

6. the luminescent layer that 4. step is obtained carries out hot curing or puts into microwave oven and carry out microwave curing;

7. reuse the UV-irradiation luminescent layer, carry out photocuring;

8. the above-mentioned light-emitting diode for preparing is encapsulated;

9. the every photoelectric properties and the parameter of test component.

7. the preparation method of light-emitting diode according to claim 6 is characterized in that, step 4. in, the luminescent layer material mixing directly is prepared on the led chip after evenly, perhaps is prepared on the led chip through behind the organic solvent diluting; Described luminescent layer be coated with by dripping, one or several modes in the spin coating, dip-coating, coating, inkjet printing, roller coat, LB film form.

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