Optical chip packaging material, preparation method and application thereof, and LED element

Abstract

The invention belongs to the technical field of LED chip packaging materials, and discloses an optical chip packaging material, a preparation method and application thereof, and an LED element. The optical chip packaging material is prepared from the following raw materials: epoxy resin, an anhydride curing agent, a polyhydroxy compound, a reaction prepolymer of dihydric alcohol, dibasic acid and 3, 4-epoxy cyclohexyl methyl 3, 4-epoxy cyclohexyl formate and / or bis ((3, 4-epoxy cyclohexyl) methyl) adipate, an antioxidant, an ultraviolet absorbent and a curing accelerator. The optical chip packaging material disclosed by the invention has the characteristics of excellent light attenuation resistance and thermal shock resistance, and can be applied to packaging of more diversified LED chips.

Description

Technical Field

[0001] The present invention relates to the technical field of LED chip packaging materials, and in particular to an optical chip packaging material, a preparation method and application thereof, and an LED element. Background Art

[0002] Light-emitting diodes (LEDs) are often considered to be a "green lighting source" that can replace traditional light sources (such as incandescent lamps and fluorescent lamps) because of their high efficiency, low energy consumption, pure light color, long life, fast response, small size, and environmental protection. The LED chip packaging material plays a certain protective role on the LED chip, among which the optical chip packaging material and packaging method determine the reliability and service life of the device.

[0003] Therefore, depending on the application requirements, there are different requirements for the high temperature resistance, UV resistance, light transmittance, refractive index, adhesion, mechanical strength and other performance of optical chip packaging materials. Such performance can be characterized by lighting aging test, light transmittance, hot and cold shock, mechanical testing machine and other testing methods. Epoxy resin packaging materials have good adhesion, sealing and mechanical strength, but they do not have advantages in UV resistance, hot and cold shock resistance, etc., which limits the application field of epoxy resin packaging materials. As the requirements for epoxy resin in LED chip packaging materials become higher and higher, it is necessary to improve its performance in light decay resistance and hot and cold shock resistance.

[0004] Japanese patent JP3442045B2 discloses an epoxy resin composition, which is widely used in various applications by using epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin to react with an anhydride curing agent. However, when the epoxy resin composition is used as an encapsulation resin, the material is easily discolored by heat due to the presence of phenyl structure in the epoxy resin, and the light decay resistance and thermal shock performance are not ideal.

[0005] US Patent No. 6989412B2 discloses an epoxy resin composition, which uses alicyclic epoxy resin and hybrid epoxy resin to improve the material's easy discoloration performance when heated to a certain extent. However, the material modulus is high after curing, and the stress generated when the temperature changes is large, and the thermal shock performance is not ideal.

[0006] Chinese patent CN105255418A discloses an epoxy resin liquid adhesive, which can obtain a flexible epoxy resin adhesive by using polyurethane-modified epoxy resin. However, the heat resistance and light resistance of polyurethane-modified epoxy resin are poor, which limits its application in optical chip packaging materials.

[0007] In addition, the prior art uses polyester polyols to toughen epoxy resins. This method has a certain toughening effect in liquid epoxy systems, but the toughening effect is not ideal in solid epoxy systems. The thermal shock resistance is poor. Summary of the invention

[0008] The technical problem to be solved by the present invention is that it is difficult for epoxy resin packaging materials in the prior art to simultaneously maintain high resistance to light decay and resistance to thermal shock. An optical chip packaging material and a preparation method thereof, and an LED component and a packaging method thereof are provided. The optical chip packaging material meets the customer's molding process and has the characteristics of resistance to light decay and resistance to thermal shock, and can be applied to high-end LED chip packaging fields such as automotive and high-end digital displays.

[0009] In order to solve the above technical problems, the first aspect of the present invention provides an optical chip packaging material, wherein the raw materials for preparing the material include epoxy resin, anhydride curing agent, polyhydroxy compound, reaction prepolymer of diol and dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, antioxidant, ultraviolet absorber and curing accelerator;

[0010] The reaction prepolymer of the diol and the dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate is obtained by reacting the diol and the dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate.

[0011] According to some embodiments of the present invention, the weight parts of each component in the raw materials for preparing the optical chip packaging material are: 50 to 800 parts of epoxy resin, preferably 100 to 550 parts; 117.6 to 201.6 parts of acid anhydride curing agent, preferably 134.4 to 184.8 parts; 11.76 to 32.26 parts of polyhydroxy compounds, preferably 18.82 to 25.87 parts; 10 to 80 parts of reaction prepolymers of diols and dibasic acids with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, preferably 30 to 60 parts; 0.1 to 5 parts of antioxidant, preferably 0.2 to 3 parts; 0.1 to 5 parts of ultraviolet absorber, preferably 0.2 to 3 parts; 0.1 to 10 parts of curing accelerator, preferably 0.4 to 4 parts.

[0012] According to some embodiments of the present invention, the epoxy equivalent of the epoxy resin is 50 to 800; preferably, the epoxy resin is selected from at least one of glycidyl ester epoxy resin, aliphatic epoxy resin, glycidyl ether epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, and naphthalene epoxy resin; further preferably, the glycidyl ester epoxy resin is selected from triglycidyl isocyanurate.

[0013] In the present invention, the epoxy resin preferably includes triglycidyl isocyanurate and aliphatic epoxy resin, which have excellent transparency and heat resistance.

[0014] According to some embodiments of the present invention, the anhydride equivalent of the anhydride curing agent is 100 to 180; preferably, the anhydride curing agent is selected from at least one of glutaric anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0015] In the present invention, the acid anhydride curing agent has good transparency and can be solid or liquid at ambient temperature. When it is solid, the acid anhydride curing agent with a softening point below 130° C. is preferred. In the present invention, the acid anhydride is the curing agent, and the polyhydroxy compound and the curing accelerator can both reduce the curing temperature of the acid anhydride curing agent and promote the curing process of the acid anhydride curing agent.

[0016] According to some embodiments of the present invention, the polyhydroxy compound is selected from polyols or polyester polyols; preferably, the polyol is selected from at least one of ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, n-pentanediol, isopentyl glycol, neopentyl glycol, 1,2-hexanediol, 1,4-cyclohexanediol, 1,6-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, trans-1,2-cyclohexanediol, 1,7-heptanediol, 1,2-heptanediol, 1,8-octanediol and 1,2-octanediol, trimethylolpropane, glycerol and pentaerythritol; the polyester polyol is selected from at least one of aliphatic polyester polyols, aromatic polyester polyols, unsaturated aliphatic polyester polyols, adipic acid-based polyester polyols and caprolactone-based polyester polyols.

[0017] According to some embodiments of the present invention, the diol is selected from at least one of ethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, and 1,4-cyclohexanedipropanol; preferably at least one of 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, and 1,4-cyclohexanedipropanol.

[0018] According to some embodiments of the present invention, the dibasic acid is selected from at least one of oxalic acid, malonic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, and 1,4-cyclohexanedipropionic acid; preferably at least one of 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, and 1,4-cyclohexanedipropionic acid.

[0019] When preparing the reaction prepolymer of the diol and dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate described in the present invention, it is preferred that the diol and the dibasic acid have the same intermediate structure, for example, 1,4-cyclohexanedimethanol and 1,4-cyclohexanedicarboxylic acid are simultaneously selected to prepare the reaction prepolymer with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate.

[0020] According to some embodiments of the present invention, the antioxidant is selected from at least one of phenolic compounds, amino compounds, organic sulfur compounds, and phosphorus compounds; preferably, the phenolic compound is selected from at least one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, 2,6-di-tert-butyl-p-cresol and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; the amino compound is selected from poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2 ,4-[(2,2,6,6,-tetramethyl-piperidinyl)imino]-1,6-hexanediol[(2,2,6,6-tetramethyl-4-piperidinyl)imino]}, butyl octylated diphenylamine; the organic sulfur compound is selected from at least one of 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 3-(dodecylthio)propionic acid-2,2-bis[[3-(dodecylthio)-propionyloxy]methyl]-1,3-propylene glycol ester; the phosphorus compound is selected from at least one of phosphite and triphenyl phosphite.

[0021] According to some embodiments of the present invention, the ultraviolet absorber is selected from at least one of a hindered amine ultraviolet absorber, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, and a triazine ultraviolet absorber; preferably, the hindered amine ultraviolet absorber is selected from at least one of tris(1,2,2,6,6-pentamethylpiperidinyl)phosphite (GW-540) and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine (light stabilizer 744); the benzophenone ultraviolet absorber is selected from at least one of 2-hydroxy-4-methoxybenzophenone (UV-9) and 2-hydroxy-4-octyloxybenzophenone (UV-531); the benzotriazole ultraviolet absorber is selected from at least one of 2-(2'-hydroxy-5'- At least one of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-octyloxyphenol (UV-1164) and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxy-phenol (UV-1577). Preferably, benzophenone ultraviolet absorbers and benzotriazole ultraviolet absorbers are used.

[0022] According to some embodiments of the present invention, the curing accelerator is selected from at least one of amines, imidazoles, organic phosphines, and substituted ureas; preferably, the amine is selected from at least one of benzyldimethylamine, NN-diethylaniline, triethylamine, and triethanolamine; the imidazole is selected from at least one of 2-ethyl-4-methylimidazole, 2-methylimidazole, and undecylimidazole; the organic phosphine is selected from at least one of triphenylphosphine, triphenylphosphine chloride, triphenylphosphine bromide, tetraphenylphosphine, benzyltriphenylphosphine bromide, and tetrabutyl O,O-diethyldithiophosphine; the substituted urea is selected from at least one of N-(2-hydroxyphenyl)-N',N'-dimethylurea, N-(4-chlorophenyl)-N',N'-dimethylurea, and N-(2-hydroxy-4-nitrobenzene)-N',N'-dimethylurea. Preferably, amines and organic phosphine compounds are used, and more preferably, organic phosphine compounds are used.

[0023] According to some embodiments of the present invention, in the preparation raw materials of the reaction prepolymer of the diol and the dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, the relationship between the epoxy equivalent in 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, the hydroxyl equivalent in the diol, and the carboxyl equivalent in the dibasic acid satisfies: [epoxy equivalent / (hydroxyl equivalent+carboxyl equivalent)] is 1.14 to 1.33, and [hydroxyl equivalent / carboxyl equivalent] is 1 to 3.

[0024] According to some embodiments of the present invention, the preparation method of the reaction prepolymer of the diol and the dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate comprises: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate is vacuumed for 1h to 4h at a temperature of 80°C to 130°C, preferably 100°C to 110°C. , preferably 2h to 3h; then after vacuuming, replacing and filling with nitrogen 3 to 15 times, preferably 5 to 10 times, adding diol and dibasic acid at the same time, and continuously filling the container with nitrogen while raising the temperature to 100°C to 140°C, preferably 115°C to 125°C, reacting for 1h to 6h, preferably 2h to 4h, to obtain a reaction prepolymer of the diol and dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate;

[0025] In the optical chip packaging material of the present invention, the weight parts of the reaction prepolymer of the diol and the dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate are 30 to 60 parts. When the reaction prepolymer of 1,4-cyclohexanedimethanol and 1,4-cyclohexanedicarboxylic acid and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate is prepared, it includes, by weight: 143.64 parts to 167.58 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 36 parts to 54 parts of 1,4-cyclohexanedimethanol, and 21.5 parts to 43 parts of 1,4-cyclohexanedicarboxylic acid; the prepared reaction prepolymer of 1,4-cyclohexanedimethanol and 1,4-cyclohexanedicarboxylic acid and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate is recorded as F1;

[0026] Alternatively, the composition comprises, by weight: 208.62 to 243.39 parts of bis((3,4-epoxycyclohexyl)methyl)adipate, 36 to 54 parts of 1,4-cyclohexanedimethanol, and 21.5 to 43 parts of 1,4-cyclohexanedicarboxylic acid; the prepared reaction prepolymer of 1,4-cyclohexanedimethanol, 1,4-cyclohexanedicarboxylic acid and bis((3,4-epoxycyclohexyl)methyl)adipate is recorded as F2.

[0027] In the present invention, the structure of the reaction prepolymer F1 is shown in the following structural formula (1):

[0028]

[0029] In formula (1), R and R' are the same or different and are independently selected from -CH2- or -CO-; n is an integer satisfying the degree of polymerization and 3≤n≤7.

[0030] In the present invention, the structure of the reaction prepolymer F2 is shown in the following structural formula (2):

[0031]

[0032] In formula (2), R and R' are the same or different and are independently selected from -CH2- or -CO-; n is an integer satisfying the degree of polymerization and 3≤n≤7.

[0033] The second aspect of the present invention provides a method for preparing the optical chip packaging material provided in the first aspect, comprising mixing the epoxy resin, anhydride curing agent, polyhydroxy compound, diol and dibasic acid in parts by weight with the reaction prepolymer of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, antioxidant, ultraviolet absorber and curing accelerator to obtain the optical chip packaging material.

[0034] According to some embodiments of the present invention, during the mixing reaction, the epoxy resin, the anhydride curing agent, the polyhydroxy compound, the diol and the dibasic acid are first heated from 20°C to 30°C to 90°C to 150°C with a heating rate of 1°C / min to 7°C / min, preferably from 20°C to 30°C to 125°C to 135°C with a heating rate of 3°C / min to 5°C / min;

[0035] Then, react at a temperature of 90°C to 150°C for 10min to 60min, preferably at a temperature of 125°C to 135°C for 20min to 40min;

[0036] Then lower the temperature to 60°C to 80°C at a cooling rate of 1°C / min to 8°C / min, preferably to 65°C to 75°C at a cooling rate of 2°C / min to 4°C / min;

[0037] Finally, a curing accelerator is added and the reaction is continued for 1 h to 10 h, preferably 3 h to 6 h, to obtain an optical chip packaging material.

[0038] According to some embodiments of the present invention, the gelation time of the optical chip packaging material at a temperature of 170° C. is 15 seconds to 70 seconds, preferably 25 seconds to 50 seconds.

[0039] The third aspect of the present invention provides the use of the optical chip packaging material described in the first aspect or the optical chip packaging material prepared by the preparation method described in the second aspect in LED chip packaging.

[0040] A fourth aspect of the present invention provides an LED element, the LED element comprising:

[0041] A substrate, an LED chip, and a molded packaging layer covering the LED chip;

[0042] Wherein, the molded packaging layer includes the optical chip packaging material described in the first aspect above or the optical chip packaging material prepared by the preparation method described in the second aspect.

[0043] A fifth aspect of the present invention provides a method for packaging an LED chip, wherein the optical chip packaging material is solidified on a substrate to which the LED is attached.

[0044] In the present invention, the packaging method is high-temperature molding curing; the conditions of the high-temperature molding curing include: curing at 170° C. for 4 minutes and then curing at 150° C. for 4 hours.

[0045] In the present invention, the LED chip is not particularly limited, and chips known in the art can be used.

[0046] Beneficial effects:

[0047] The 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate used in the optical chip packaging material provided by the present invention is a flexible alicyclic epoxy resin having excellent heat resistance and light resistance; the diol (especially 1,4-cyclohexanedimethanol) and the dibasic acid (especially 1,4-cyclohexanedicarboxylic acid) have excellent heat resistance and light resistance and also have a good rigid structure; the 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3 The reaction prepolymer obtained by the reaction of 4-epoxycyclohexyl)methyl)adipate with diols and dibasic acids can introduce flexible chain segments to play a buffering role, thereby improving the toughness of the material while ensuring good strength of the material, and enhancing the high impact resistance of the optical chip packaging material; at the same time, it does not reduce the light decay resistance of the packaging material, ensuring that the packaging material is resistant to light and high temperature discoloration, and has good light and heat resistance; in addition, by adding additives such as antioxidants and ultraviolet absorbers, the weather resistance of the packaging material is improved, and the light decay resistance of the optical chip packaging material is further enhanced.

[0048] The present invention screens raw materials and processes, and while ensuring the material's resistance to light decay, adds a long-chain, light-resistant, high-temperature discoloration-resistant, and reactive reaction prepolymer to improve the cold and heat shock resistance of the packaging material. At the same time, a matching UV absorber and antioxidant are added. The UV absorber reduces the damage of UV rays to objects by absorbing and converting UV energy, thereby improving the material's UV resistance; the antioxidant eliminates free radicals generated by light or high temperature to prevent them from inducing further oxidation reactions, thereby enhancing the material's weather resistance and light decay resistance without affecting the above-mentioned properties of the material.

[0049] The optical chip packaging material provided by the present invention has the characteristics of excellent light decay resistance and thermal shock resistance, and can be applied to more diversified LED chip packaging. DETAILED DESCRIPTION

[0050] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited by these embodiments.

[0051] In the following examples and comparative examples of the present invention, unless otherwise specified, all raw materials used are commercially available.

[0052] In the following embodiments of the present invention, different types of toughening agents are added to compare the performance of the products. The compatibility and reactivity of the toughening agent with the epoxy resin system will affect the performance of the product. In the present invention, the toughening agent is selected from one or more of a bifunctional epoxy resin active toughening diluent and a polyester polyol to examine the light decay resistance and thermal shock resistance of the obtained optical chip packaging material.

[0053] In the following examples and comparative examples:

[0054] Epoxy resin A1 is triglycidyl isocyanurate (epoxy equivalent 100), Nissan Chemical Co., Ltd.;

[0055] Epoxy resin A2 is bisphenol A epoxy resin (epoxy equivalent weight 550), Dow Chemical Company;

[0056] Anhydride curing agent B is methyl hexahydrophthalic anhydride (anhydride equivalent weight is 168), New Japan Chemical Co., Ltd.;

[0057] Polyol C is neopentyl glycol, TCI;

[0058] 3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, Daicel Corporation;

[0059] Bis((3,4-epoxycyclohexyl)methyl)adipate, Jiangsu Taitel;

[0060] 1,4-cyclohexanedimethanol, TCI;

[0061] 1,4-cyclohexanedicarboxylic acid, TCI;

[0062] Toughener G1 is PCL220N polycaprolactone polyol, Daicel Corporation;

[0063] Toughener G2 is polyethylene glycol diglycidyl ether, TCI;

[0064] Antioxidant H1 is 2,6-di-tert-butyl-p-cresol, which is similar to Nanjing;

[0065] The antioxidant H2 is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, TCI;

[0066] Antioxidant H3 is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which is similar to that in Nanjing;

[0067] The UV absorber I1 is 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, TCI;

[0068] The UV absorber I2 is 2-hydroxy-4-methoxybenzophenone, TCI;

[0069] Curing accelerator J is tetrabutyl O,O-diethylphosphonodithioic acid, produced by Nippon Chemical Industry Co., Ltd.

[0070] Examples 1-13

[0071] This embodiment is used to illustrate the optical chip packaging material and the preparation method thereof of the present invention.

[0072] According to the weight parts described in Table 1, the reaction prepolymer of epoxy resin, anhydride curing agent, polyhydroxy compound, diol and dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, antioxidant and ultraviolet absorber were first heated from 25°C to 130°C at a heating rate of 4°C / min; then reacted at a temperature of 130°C for 30min; then the temperature was reduced to 70°C at a cooling rate of 3°C / min; a curing accelerator was added and the reaction was continued for 5h to obtain an optical chip packaging material.

[0073] The reaction degree of the optical chip packaging materials prepared in the above Examples 1-13, that is, the gelation time of the optical chip packaging materials placed at 170° C. is shown in Table 2.

[0074] Table 1

[0075]

[0076] In Table 1, the preparation method of the reaction prepolymer F1 is as follows: 143.64 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate are vacuumed for 3 hours at a temperature of 100°C; after vacuuming and replacing with nitrogen for 5 times, 50.4 parts of 1,4-cyclohexanedimethanol and 25.8 parts of 1,4-cyclohexanedicarboxylic acid are added simultaneously, and nitrogen is continuously charged into the container while the temperature is raised to 120°C, and the reaction is carried out for 3 hours to obtain the reaction prepolymer F1. Among them, the relationship between the epoxy equivalent in 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate, the hydroxyl equivalent in 1,4-cyclohexanedimethanol, and the carboxyl equivalent in 1,4-cyclohexanedicarboxylic acid satisfies: [epoxy equivalent / (hydroxyl equivalent+carboxyl equivalent)] is 1.14, and [hydroxyl equivalent / carboxyl equivalent] is 2.33.

[0077] In Table 1, the preparation method of the reaction prepolymer F2 is as follows: 208.62 parts of bis((3,4-epoxycyclohexyl)methyl)adipate are vacuumed for 3 hours at a temperature of 100°C; after vacuuming and replacing with nitrogen for 5 times, 50.4 parts of 1,4-cyclohexanedimethanol and 25.8 parts of 1,4-cyclohexanedicarboxylic acid are added simultaneously, and nitrogen is continuously charged into the container while the temperature is raised to 120°C, and the reaction is carried out for 3 hours to obtain the reaction prepolymer F2. Among them, the relationship between the epoxy equivalent in bis((3,4-epoxycyclohexyl)methyl)adipate, the hydroxyl equivalent in 1,4-cyclohexanedimethanol, and the carboxyl equivalent in 1,4-cyclohexanedicarboxylic acid satisfies: [epoxy equivalent / (hydroxyl equivalent+carboxyl equivalent)] is 1.14, and [hydroxyl equivalent / carboxyl equivalent] is 2.33.

[0078] Table 2

[0079]

[0080] Comparative Examples 1-13

[0081] This comparative example is used to illustrate the optical chip packaging material and the preparation method thereof of the present invention.

[0082] The preparation method is the same as that of Example 1-13, except that the types of raw materials and their weight parts are as described in Table 3.

[0083] The reaction degree of the optical chip packaging materials prepared in Comparative Examples 1-13, i.e., the gelation time of the optical chip packaging materials placed at 170° C., is shown in Table 4.

[0084] Table 3

[0085]

[0086]

[0087] In Table 3, the preparation method of the reaction prepolymer D is as follows: 208.62 parts of bis((3,4-epoxycyclohexyl)methyl)adipate are vacuumed at a temperature of 100°C for 3 hours; after vacuuming and replacing with nitrogen for 5 times, 72 parts of 1,4-cyclohexanedimethanol are added, and the container is continuously filled with nitrogen while the temperature is raised to 120°C, and the reaction is carried out for 3 hours to obtain the reaction prepolymer D. Among them, the relationship between the epoxy equivalent in bis((3,4-epoxycyclohexyl)methyl)adipate and the hydroxyl equivalent in 1,4-cyclohexanedimethanol satisfies: [epoxy equivalent / hydroxyl equivalent] is 1.14.

[0088] In Table 3, the preparation method of the reaction prepolymer E is as follows: 208.62 parts of bis((3,4-epoxycyclohexyl)methyl)adipate are vacuumed at a temperature of 100°C for 3 hours; after vacuuming and replacing with nitrogen for 5 times, 86 parts of 1,4-cyclohexanedicarboxylic acid are added, and the container is continuously filled with nitrogen while the temperature is raised to 115°C, and the reaction is carried out for 1 hour to obtain the reaction prepolymer E. Among them, the relationship between the epoxy equivalent in bis((3,4-epoxycyclohexyl)methyl)adipate and the carboxyl equivalent in 1,4-cyclohexanedicarboxylic acid satisfies: [epoxy equivalent / carboxyl equivalent] is 1.14.

[0089] In Table 3, the preparation method of the reaction prepolymer F3 is as follows: 146.4 parts of bis((3,4-epoxycyclohexyl)methyl)adipate are vacuumed for 3 hours at a temperature of 100°C; after vacuuming and replacing with nitrogen for 5 times, 50.4 parts of 1,4-cyclohexanedimethanol and 25.8 parts of 1,4-cyclohexanedicarboxylic acid are added simultaneously, and nitrogen is continuously charged into the container while the temperature is raised to 115°C, and the reaction is carried out for 1 hour to obtain the reaction prepolymer F3. Among them, the relationship between the epoxy equivalent in bis((3,4-epoxycyclohexyl)methyl)adipate, the hydroxyl equivalent in 1,4-cyclohexanedimethanol, and the carboxyl equivalent in 1,4-cyclohexanedicarboxylic acid satisfies: [epoxy equivalent / (hydroxyl equivalent+carboxyl equivalent)] is 0.8, and [hydroxyl equivalent / carboxyl equivalent] is 2.33.

[0090] In Table 3, the preparation method of the reaction prepolymer F4 is as follows: 274.5 parts of bis((3,4-epoxycyclohexyl)methyl)adipate are vacuumed for 3 hours at a temperature of 100°C; after vacuuming and replacing with nitrogen for 5 times, 50.4 parts of 1,4-cyclohexanedimethanol and 25.8 parts of 1,4-cyclohexanedicarboxylic acid are added, and nitrogen is continuously charged into the container while the temperature is raised to 120°C, and the reaction is carried out for 3 hours to obtain the reaction prepolymer F4. Among them, the relationship between the epoxy equivalent in bis((3,4-epoxycyclohexyl)methyl)adipate, the hydroxyl equivalent in 1,4-cyclohexanedimethanol, and the carboxyl equivalent in 1,4-cyclohexanedicarboxylic acid satisfies: [epoxy equivalent / (hydroxyl equivalent+carboxyl equivalent)] is 1.5, and [hydroxyl equivalent / carboxyl equivalent] is 2.33.

[0091] In Table 3, the preparation method of the reaction prepolymer F5 is as follows: 208.62 parts of bis((3,4-epoxycyclohexyl)methyl)adipate are vacuumed at a temperature of 100°C for 3 hours; after vacuuming and replacing with nitrogen for 5 times, 24 parts of 1,4-cyclohexanedimethanol and 57.33 parts of 1,4-cyclohexanedicarboxylic acid are added, and nitrogen is continuously charged into the container while the temperature is raised to 115°C, and the reaction is carried out for 1 hour to obtain the reaction prepolymer F5. Among them, the relationship between the epoxy equivalent in bis((3,4-epoxycyclohexyl)methyl)adipate, the hydroxyl equivalent in 1,4-cyclohexanedimethanol, and the carboxyl equivalent in 1,4-cyclohexanedicarboxylic acid satisfies: [epoxy equivalent / (hydroxyl equivalent+carboxyl equivalent)] is 1.14, and [hydroxyl equivalent / carboxyl equivalent] is 0.5.

[0092] In Table 3, the preparation method of the reaction prepolymer F6 is as follows: 208.62 parts of bis((3,4-epoxycyclohexyl)methyl)adipate are vacuumed for 3 hours at a temperature of 100°C; after vacuuming and replacing with nitrogen for 5 times, 57.6 parts of 1,4-cyclohexanedimethanol and 17.2 parts of 1,4-cyclohexanedicarboxylic acid are added, and nitrogen is continuously charged into the container while the temperature is raised to 120°C, and the reaction is carried out for 3 hours to obtain the reaction prepolymer F6. Among them, the relationship between the epoxy equivalent in bis((3,4-epoxycyclohexyl)methyl)adipate, the hydroxyl equivalent in 1,4-cyclohexanedimethanol, and the carboxyl equivalent in 1,4-cyclohexanedicarboxylic acid satisfies: [epoxy equivalent / (hydroxyl equivalent+carboxyl equivalent)] is 1.14, and [hydroxyl equivalent / carboxyl equivalent] is 4.

[0093] Table 4

[0094]

[0095] Since the packaging materials used for LED chip packaging require high light transmittance of the finished product, which limits the application of materials with poor compatibility with the epoxy system, only the finished products with good transparency are tested for performance.

[0096] To further illustrate the advancement of the present invention, the transparency, light decay resistance and thermal shock resistance of the optical chip packaging materials prepared in the above Examples 1-14 and Comparative Examples 1-12 are measured and evaluated by the following method:

[0097] (I) Light decay resistance at 25°C

[0098] The optical chip packaging materials prepared in Examples 1-14 and Comparative Examples 1-12 were packaged into LED chips by high-temperature molding curing (cured at 170°C for 4 minutes and then at 150°C for 4 hours) to obtain 0603 SMD LED lamp beads. The LED lamp beads were clamped on a SMD aging instrument (AN208C, Shenzhen Anode Technology Co., Ltd.), and lit at a current of 10 mA at a temperature of 25°C. The light intensity maintenance rate at 500 hours and 1000 hours was tested and recorded. The statistical results are shown in Table 5.

[0099] A high-precision fast spectroradiometer (HAAS-2000, Hangzhou Yuanfang Optoelectronic Information Co., Ltd.) was used to test and calculate the light intensity maintenance rate.

[0100] (II) Light decay resistance at 85°C

[0101] The optical chip packaging materials prepared in Examples 1-14 and Comparative Examples 1-12 were packaged into LED chips by high-temperature molding curing (cured at 170°C for 4 minutes and then at 150°C for 4 hours) to obtain 0603 SMD LED lamp beads. The LED lamp beads were clamped on a SMD aging instrument (AN207B, Shenzhen Anode Technology Co., Ltd.), placed in an oven at 85°C, lit with a current of 10 mA, and the light intensity maintenance rate at 500 hours and 1000 hours was tested and recorded. The statistical results are shown in Table 5.

[0102] A high-precision fast spectroradiometer (HAAS-2000, Hangzhou Yuanfang Optoelectronic Information Co., Ltd.) was used to test and calculate the light intensity maintenance rate.

[0103] (III) Light decay resistance at 85°C and 85%RH

[0104] The optical chip packaging materials prepared in Examples 1-14 and Comparative Examples 1-12 were packaged into LED chips by high-temperature molding curing (cured at 170°C for 4 minutes and then at 150°C for 4 hours) to obtain 0603 SMD LED lamp beads. The LED lamp beads were clamped on a SMD aging instrument (AN207B, Shenzhen Anode Technology Co., Ltd.), and placed in a constant temperature and humidity tester (85°C, 85% RH), and lit with a current of 10mA. The light intensity maintenance rate at 500h and 1000h was tested and recorded. The statistical results are shown in Table 5.

[0105] A high-precision fast spectroradiometer (HAAS-2000, Hangzhou Yuanfang Optoelectronic Information Co., Ltd.) was used to test and calculate the light intensity maintenance rate.

[0106] (IV) Thermal shock resistance test:

[0107] The optical chip packaging materials prepared in Examples 1-14 and Comparative Examples 1-12 were packaged into LED chips by high-temperature molding and curing (cured at 170°C for 4 minutes, and then cured at 150°C for 4 hours) to obtain 0603 SMD LED lamp beads. The LED lamp beads were placed in a hot and cold shock test chamber (ESPEC, Japan, TSE11A), and the test parameters were set as follows: 150°C in the high temperature zone, -65°C in the low temperature zone, and one cycle every 14 minutes. The number of dead lamps was recorded every 100 impacts. If the number of lamp beads that did not light up did not exceed 5‰, they were put back into the test chamber and continued to be tested until the number of dead lamps exceeded 5‰. The test was then stopped and the cumulative number of impacts was recorded. The results are statistically shown in Table 5.

[0108] Table 5

[0109]

[0110]

[0111] The performance data in Table 5 above show that the optical chip packaging material of the present invention containing the reaction prepolymer of diol and dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate has excellent light decay resistance and thermal shock resistance, and can be applied to more diversified LED chip packaging; and the relationship between the epoxy equivalent in 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate in the reaction prepolymer, the hydroxyl equivalent in 1,4-cyclohexanedimethanol, and the carboxyl equivalent in 1,4-cyclohexanedicarboxylic acid satisfies: when [epoxy equivalent / (hydroxyl equivalent+carboxyl equivalent)] is 1.14-1.33, and [hydroxyl equivalent / carboxyl equivalent] is 1-3, the light decay resistance and thermal shock resistance of the LED chip packaging product can be significantly improved.

[0112] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. An optical chip packaging material, characterized in that: The raw materials for preparing the optical chip packaging material include epoxy resin, anhydride curing agent, polyhydroxy compound, reaction prepolymer of diol and dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, antioxidant, ultraviolet absorber and curing accelerator; The reaction prepolymer of the diol and the dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate is obtained by reacting the diol and the dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate.

2. The optical chip packaging material according to claim 1, characterized in that: The weight parts of each component in the raw materials for preparing the optical chip packaging material are: 50 to 800 parts of epoxy resin, preferably 100 to 550 parts; 117.6 to 201.6 parts of acid anhydride curing agent, preferably 134.4 to 184.8 parts; 11.76 to 32.26 parts of polyhydroxy compound, preferably 18.82 to 25.87 parts; 10 to 80 parts of reaction prepolymer of diol and dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, preferably 30 to 60 parts; 0.1 to 5 parts of antioxidant, preferably 0.2 to 3 parts; 0.1 to 5 parts of ultraviolet absorber, preferably 0.2 to 3 parts; 0.1 to 10 parts of curing accelerator, preferably 0.4 to 4 parts.

3. The optical chip packaging material according to claim 1 or 2, characterized in that: The epoxy equivalent of the epoxy resin is 50 to 800; preferably, the epoxy resin is selected from at least one of glycidyl ester epoxy resin, aliphatic epoxy resin, glycidyl ether epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, and naphthalene epoxy resin; further preferably, the glycidyl ester epoxy resin is selected from triglycidyl isocyanurate; And / or, the anhydride equivalent of the acid anhydride curing agent is 100 to 180; preferably, the acid anhydride curing agent is selected from at least one of glutaric anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride; And / or, the polyhydroxy compound is selected from polyols or polyester polyols; preferably, the polyol is selected from at least one of ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, n-pentanediol, isopentyl glycol, neopentyl glycol, 1,2-hexanediol, 1,4-cyclohexanediol, 1,6-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, trans-1,2-cyclohexanediol, 1,7-heptanediol, 1,2-heptanediol, 1,8-octanediol and 1,2-octanediol, trimethylolpropane, glycerol and pentaerythritol; the polyester polyol is selected from at least one of aliphatic polyester polyols, aromatic polyester polyols, unsaturated aliphatic polyester polyols, adipic acid polyester polyols and caprolactone polyester polyols; And / or, the diol is at least one selected from ethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, and 1,4-cyclohexanedipropanol; And / or, the dibasic acid is at least one selected from oxalic acid, malonic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, and 1,4-cyclohexanedipropionic acid; And / or, the antioxidant is selected from at least one of phenolic compounds, amino compounds, organic sulfur compounds, and phosphorus compounds; preferably, the phenolic compound is selected from at least one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, 2,6-di-tert-butyl-p-cresol and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; the amino compound is selected from poly{[6-[(1,1,3,3-tetramethylbutyl)amino]]-1,3,5-triazine-2,4-[( At least one of 2,2,6,6-tetramethyl-piperidinyl)imino]-1,6-hexanediol [(2,2,6,6-tetramethyl-4-piperidinyl)imino]}, butyl octylated diphenylamine; the organic sulfur compound is selected from at least one of 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 3-(dodecylthio)propionic acid-2,2-bis[[3-(dodecylthio)-propionyloxy]methyl]-1,3-propylene glycol ester; the phosphorus compound is selected from at least one of phosphite and triphenyl phosphite; And / or, the ultraviolet absorber is selected from at least one of hindered amine ultraviolet absorbers, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and triazine ultraviolet absorbers; preferably, the hindered amine ultraviolet absorber is selected from at least one of tris (1,2,2,6,6-pentamethylpiperidinyl) phosphite and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine; the benzophenone ultraviolet absorber is selected from at least one of 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-octyloxybenzophenone; the benzotriazole ultraviolet absorber is selected from at least one of 2-(2'-hydroxy -5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole; the triazine ultraviolet absorber is selected from at least one of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-octyloxyphenol and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxy-phenol; And / or, the curing accelerator is selected from at least one of amines, imidazoles, organic phosphines, and substituted ureas; preferably, the amines are selected from at least one of benzyldimethylamine, NN-diethylaniline, triethylamine, and triethanolamine; the imidazoles are selected from at least one of 2-ethyl-4-methylimidazole, 2-methylimidazole, and undecylimidazole; the organic phosphines are selected from at least one of triphenylphosphine, triphenylphosphine chloride, triphenylphosphine bromide, tetraphenylphosphine, benzyltriphenylphosphine bromide, and tetrabutyl O,O-diethyldithiophosphine; the substituted ureas are selected from at least one of N-(2-hydroxyphenyl)-N',N'-dimethylurea, N-(4-chlorophenyl)-N',N'-dimethylurea, and N-(2-hydroxy-4-nitrobenzene)-N',N'-dimethylurea.

4. The optical chip packaging material according to any one of claims 1 to 3, characterized in that: In the preparation raw materials of the reaction prepolymer of the diol and the dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, the relationship between the epoxy equivalent in 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, the hydroxyl equivalent in the diol, and the carboxyl equivalent in the dibasic acid satisfies: [epoxy equivalent / (hydroxyl equivalent+carboxyl equivalent)] is 1.14 to 1.33, and [hydroxyl equivalent / carboxyl equivalent] is 1 to 3.

5. The optical chip packaging material according to any one of claims 1 to 4, characterized in that: The method for preparing the reaction prepolymer of the diol and the dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate comprises: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate is vacuumized at a temperature of 80° C. to 130° C., preferably 100° C. to 110° C. for 1 h to 4 h, preferably 2 h. ~3h; then after vacuuming, replacing and filling with nitrogen 3 to 15 times, preferably 5 to 10 times, add diol and dibasic acid, and continue to fill the container with nitrogen while raising the temperature to 100°C to 140°C, preferably 115°C to 125°C, and react for 1h to 6h, preferably 2h to 4h to obtain a reaction prepolymer of the diol and dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate.

6. A method for preparing an optical chip packaging material according to any one of claims 1 to 5, characterized in that: The method comprises mixing and reacting the epoxy resin, anhydride curing agent, polyhydroxy compound, diol and dibasic acid in parts by weight with the reaction prepolymer of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, antioxidant, ultraviolet absorber and curing accelerator to obtain the optical chip packaging material.

7. The preparation method according to claim 6, characterized in that: During the mixing reaction, the reaction prepolymer of epoxy resin, anhydride curing agent, polyhydroxy compound, diol and dibasic acid with 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and / or bis((3,4-epoxycyclohexyl)methyl)adipate, antioxidant and ultraviolet absorber are first heated from 20°C to 30°C to 90°C to 150°C at a heating rate of 1°C / min to 7°C / min, preferably from 20°C to 30°C to 125°C to 135°C at a heating rate of 3°C / min to 5°C / min; Then, react at a temperature of 90°C to 150°C for 10min to 60min, preferably at a temperature of 125°C to 135°C for 20min to 40min; Then lower the temperature to 60°C to 80°C at a cooling rate of 1°C / min to 8°C / min, preferably to 65°C to 75°C at a cooling rate of 2°C / min to 4°C / min; Finally, a curing accelerator is added and the reaction is continued for 1 h to 10 h, preferably 3 h to 6 h, to obtain an optical chip packaging material.

8. The preparation method according to claim 6 or 7, characterized in that: The gelation time of the optical chip packaging material at a temperature of 170° C. is 15 seconds to 70 seconds, preferably 25 seconds to 50 seconds.

9. Use of the optical chip packaging material according to any one of claims 1 to 5 or the optical chip packaging material prepared by the preparation method according to any one of claims 6 to 8 in LED chip packaging.

10. An LED element, characterized in that: The LED element comprises: A substrate, an LED chip, and a molded packaging layer covering the LED chip; Wherein, the molded packaging layer comprises the optical chip packaging material according to any one of claims 1 to 5 or the optical chip packaging material prepared by the preparation method according to any one of claims 6 to 8.

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