An optical chip packaging material, a preparation method and applications thereof

Abstract

An optical chip packaging material, the preparation raw materials of the optical chip packaging material include: 50-800 parts by weight of epoxy resin, 10-500 parts by weight of organic silicon hybrid resin, 130-185 parts by weight of anhydride curing agent, 5-20 parts by weight of polyhydroxy compound; the preparation method of the organic silicon hybrid resin includes: under acidic conditions, methyl trialkoxysilane, phenyl trialkoxysilane and silane coupling agent are subjected to hydrolysis reaction to obtain an aqueous phase and an organic phase, monohydroxy-terminated silicone oil is added to the organic phase and then subjected to condensation reaction; the number of carbon atoms of the alkoxy group in the methyl trialkoxysilane is 1-4; the number of carbon atoms of the alkoxy group in the phenyl trialkoxysilane is 1-4. The organic silicon hybrid resin of the application can better react with the epoxy resin, so that the obtained optical chip packaging material can have enhanced heat-resistant stability and light decay resistance, can significantly reduce modulus reduction stress, and can improve the reflow soldering performance of the packaging material.

Description

TECHNICAL FIELD

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

[0002] Light-emitting diodes (LEDs) and other optical semiconductor elements have high efficiency, low energy consumption, wide dimming range, long service life, green environmental protection, safety and reliability, etc. compared with traditional light sources (such as incandescent lamps and fluorescent lamps), and have simple structure and small size. In addition, the structure does not contain glass, filament and other easily damaged components, which can reduce the pollution of waste to the environment. Therefore, as a new generation of green environmental protection products, it is widely used in the fields of automobiles, traffic signal lamps, lighting, electronic device backlights and the like.

[0003] LED chip packaging is a key link in the manufacturing process of LEDs, which has a profound impact on the performance and application effect of LED products. The packaging material mainly plays the role of sealing and protecting the chip to work normally, avoiding the damage of external environment to the chip; in addition, the packaging material can fix and support the wires to prevent the electronic components from being mechanically damaged by vibration, impact and the like; at the same time, appropriate packaging material and reasonable packaging structure can enhance the light efficiency and heat dissipation performance of the LED. Therefore, the LED chip packaging material should have good sealing property, light transmission, adhesion, dielectric property and mechanical property. According to the different application scenarios, there are different degrees of demand for the performance of the packaging material.

[0004] Epoxy resin packaging material has good sealing property, adhesion, dielectric property and mechanical property, and low cost, flexible formula and high production efficiency, so it accounts for a considerable proportion in the LED chip packaging market. However, due to its poor weather resistance and problems such as brittleness, fatigue, and large curing stress, the service life of LED devices is reduced, which limits the application field of epoxy resin packaging material. For example, in the field of high-end electrical appliances, the use of epoxy resin packaging material has the risk of dead lamp after 260℃ reflow soldering. With the development and power improvement of LEDs, higher requirements are put forward for the packaging material for LED chips, such as improving the heat resistance, light decay resistance, reducing the stress, and improving the reflow soldering dead lamp resistance, etc.

[0005] Compared with epoxy resin, silicone material has good thermal stability, excellent ultraviolet aging resistance and low internal stress, but also has the disadvantages of low adhesion, poor mechanical property, low glass transition temperature and easy softening deformation at high temperature. In addition, the combination application of epoxy resin and silicone material is limited by the chemical incompatibility of the two, and simple blending does not make the performance better. SUMMARY

[0006] In order to solve the above problems in the prior art, the application provides an optical chip packaging material, a preparation method and application. The packaging material has the characteristics of light decay resistance, low stress, and reflow soldering dead lamp resistance, and can be applied to more diversified LED chip packaging fields.

[0007] In a first aspect, the application provides an optical chip packaging material, and preparation raw materials of the optical chip packaging material include, by weight fraction, 50-800 parts of an epoxy resin, 10-500 parts of an organic silicon hybrid resin, 130-185 parts of an acid anhydride curing agent, and 5-20 parts of a polyhydroxy compound.

[0008] The preparation method of the organic silicon hybrid resin includes: under an acidic condition, methyl trialkoxysilane and phenyl trialkoxysilane are subjected to a hydrolysis reaction to obtain an aqueous phase and an organic phase, monohydroxyl-terminated silicone oil is added to the organic phase, and then a condensation reaction is performed.

[0009] The number of carbon atoms of the alkoxy group in the methyl trialkoxysilane is 1-4.

[0010] The number of carbon atoms of the alkoxy group in the phenyl trialkoxysilane is 1-4.

[0011] The specific organic silicon hybrid resin provided by the application contains an epoxy group in the organic silicon hybrid resin group. The epoxy group in the organic silicon hybrid resin can increase the reactivity of the organic silicon hybrid resin and the epoxy resin. The organic silicon hybrid resin and the epoxy resin have good compatibility, so that the active groups of the two materials can better react to form a homogeneous organic silicon hybrid epoxy material.

[0012] As a specific embodiment of the application, by weight fraction, the raw materials for preparing the organic silicon hybrid resin include: 800-910 parts of methyl trialkoxysilane, 700-900 parts of phenyl trialkoxysilane, 50-100 parts of a silane coupling agent, and 50-90 parts of monohydroxyl-terminated silicone oil.

[0013] As a specific embodiment of the application, by weight fraction, the optical chip packaging material includes:

[0014] The epoxy resin is 100-550 parts;

[0015] The organic silicon hybrid resin is 30-400 parts;

[0016] The acid anhydride curing agent is 130-170 parts;

[0017] The polyhydroxy compound is 7-16 parts;

[0018] The antioxidant is 0.1-5 parts, preferably 0.2-3 parts;

[0019] 0.1 to 5 parts, preferably 0.2 to 3 parts.

[0020] As a specific embodiment of the present application, the silane coupling agent is selected from γ-glycidoxypropylmethyldimethoxysilane or β(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0021] As a specific embodiment of the present application, the molecular formula of the monohydroxyl terminated silicone oil is shown as formula (1):

[0022] Formula (1),

[0023] In formula (1), R 1 , R 2 are each independently selected from C1-C6 monovalent alkyl, preferably selected from methyl, ethyl or propyl;

[0024] n is a natural number of 3-8.

[0025] The organic silicon hybrid resin of the present application contains , contains the organic silicon hybrid resin with the group has better flexibility and crosslinking density. Meanwhile, the organic silicon hybrid resin in the present application contains the group, which can ensure the dispersibility, stability and heat resistance of the whole system to meet the requirements.

[0026] Specifically, the preparation method of the organic silicon hybrid resin comprises:

[0027] (1) mixing methyltrimethoxysilane, phenyltrimethoxysilane, a silane coupling agent and an organic solvent, stirring at a speed of 200-600 rpm for 10 min-60 min, preferably 15 min-35 min, to form a first mixed solution;

[0028] (2) mixing the first mixed solution with a second mixed solution at a temperature of 20-70°C, preferably 25-45°C, and carrying out a hydrolysis reaction at a temperature of 68-78°C, preferably 70-75°C, and keeping the solution in a reflux state, for 3-7 h, preferably 4-6 h, to obtain a hydrolysis reaction product, the second mixed solution being an inorganic acid solution;

[0029] (3) placing the hydrolysis reaction product at 2-30°C, preferably 5-15°C, for 6-24 h, preferably 10-14 h, to separate the hydrolysis reaction product into an organic phase and an aqueous phase; mixing the organic phase with a monohydroxyl terminated silicone oil at 70-90°C, preferably 75-85°C, to carry out a condensation reaction, for 1-4 h, preferably 2-3 h; and removing the remaining solvent and low-boiling substances by reduced pressure distillation at 100-140°C, preferably 115-130°C, to obtain the organic silicon hybrid resin.

[0030] As a specific embodiment of the present application, the epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, glycidyl ester type epoxy resin, glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin.

[0031] Preferably, the epoxy resin is selected from one or more of bisphenol A type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin.

[0032] As a specific embodiment of the present application, the anhydride curing agent is selected from one or more of phthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, maleic anhydride, pyromellitic anhydride, trimellitic anhydride, glutaric anhydride, tung oil anhydride, hexachloro endomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, 1,2,3,4-cyclopentane tetra carboxylic dianhydride and methylcyclohexene tetra carboxylic dianhydride.

[0033] Preferably, the anhydride curing agent is selected from one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or methyl hexahydrophthalic anhydride.

[0034] As a specific embodiment of the present application, the polyhydroxy compound is selected from one or more of polyhydric alcohol, polyester polyhydric alcohol or polyether polyhydric alcohol.

[0035] In the present application, the hydroxyl group in the polyhydroxy compound reacts with the anhydride curing agent, so that the anhydride curing agent can better react with the epoxy resin, and at the same time the polyhydroxy compound itself is a chain extender, so that a relatively good long chain structure can be obtained.

[0036] Preferably, the polyhydric alcohol is selected from one or more of ethylene glycol, diethylene glycol, glycerol, 1,3-butylene glycol, 1,4-butylene glycol, n-pentanediol, neopentyl glycol, isopentanediol, 1,2-hexanediol, 1,4-cyclohexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, trimethylolpropane, pentaerythritol.

[0037] Preferably, the polyester polyhydric alcohol is selected from one or more of aromatic polyester polyhydric alcohol, aliphatic polyester polyhydric alcohol, unsaturated aliphatic polyester polyhydric alcohol, adipic acid-based polyester polyhydric alcohol.

[0038] Preferably, the polyether polyhydric alcohol is selected from one or more of polyether dihydric alcohol or polyether trihydric alcohol with a molecular weight of 500-2000.

[0039] Specifically, the polyhydroxy compound is selected from one or more of ethylene glycol, glycerol, 1,4-butylene glycol and neopentyl glycol.

[0040] As a specific embodiment of the present application, the antioxidant is selected from one or more of an amine compound, a phosphorus compound, an organic sulfur compound, and a phenol compound.

[0041] Preferably, the amine compound is selected from one or more of butyloctylated diphenylamine, poly{[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-[(2,2,6,6-tetramethylpiperidyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino]}.

[0042] Preferably, the phosphorus compound is selected from one or both of a phosphite and triphenyl phosphite.

[0043] Preferably, the organic sulfur compound is selected from one or both of 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 3-(dodecylthio)propionic acid 2,2-bis[[3-(dodecylthio)propionyloxy]methyl]-1,3-propanediol ester.

[0044] Preferably, the phenol compound is selected from one or more of 2,6-di-tert-butyl-p-cresol, pentaerythrityl tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and n-octadecanol β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0045] In particular, the antioxidant is selected from one or more of a phosphorus compound and a phenol compound.

[0046] As a specific embodiment of the present application, the ultraviolet absorber is selected from one or more of a hindered amine ultraviolet absorber, a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, and a triazine ultraviolet absorber.

[0047] Preferably, the hindered amine ultraviolet absorber is selected from one or both of tris(1,2,2,6,6-pentamethylpiperidyl) phosphite (Chimassorb® 770) and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine (Hostavin® 744).

[0048] Preferably, the benzotriazole ultraviolet absorber is selected from one or more of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (Cyasorb® UV-P), 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole (Cyasorb® UV-326), 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole (Cyasorb® UV-327), and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (Cyasorb® UV-329).

[0049] Preferably, the benzophenone ultraviolet absorber is selected from one or both of 2-hydroxy-4-methoxybenzophenone (UV-9) and 2-hydroxy-4-n-octyloxybenzophenone (UV-531).

[0050] Preferably, the triazine ultraviolet absorber is selected from one or both of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-octyloxyphenol (UV-1164) and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol (UV-1577).

[0051] In particular, the ultraviolet absorber is selected from one or more of benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers.

[0052] In a second aspect, the present application provides a preparation method of the optical chip packaging material provided in the first aspect of the present application. The epoxy resin, the silicone hybrid resin, the anhydride curing agent, and the polyhydroxy compound are mixed to obtain the optical chip packaging material.

[0053] As a specific embodiment of the present application, the mixing step comprises:

[0054] (1) The epoxy resin, the silicone hybrid resin, the anhydride curing agent, the polyhydroxy compound, the antioxidant, and the ultraviolet absorber are mixed and reacted at 90-150°C for 10-60 minutes.

[0055] (2) The accelerator and the catalyst are added, and the reaction is continued at 60-80°C for 1-12 hours to obtain the optical chip packaging material.

[0056] In particular, the epoxy resin, the silicone hybrid resin, the anhydride curing agent, the polyhydroxy compound, the antioxidant, and the ultraviolet absorber are raised from 20-30°C to 90-150°C at a rate of 1-7°C / min, preferably from 20-30°C to 125-135°C at a rate of 3-5°C / min.

[0057] Then the reaction is carried out at 90-150°C for 10-60 minutes, preferably at 125-135°C for 20-40 minutes; the temperature is then lowered to 60-80°C at a rate of 1-8°C / min, preferably to 65-75°C at a rate of 2-4°C / min; the accelerator and the catalyst are added, and the reaction is continued for 1-12 hours, preferably for 4-8 hours, to obtain the optical chip packaging material.

[0058] As some embodiments of the present application, the optical chip packaging material has a gelation time of 15 seconds to 70 seconds, preferably 25 seconds to 50 seconds, at a temperature of 170°C.

[0059] As some embodiments of the present application, the raw materials for preparing the optical chip packaging material include, by weight fraction:

[0060] epoxy resin 100 parts to 550 parts;

[0061] silicone hybrid resin 30 parts to 400 parts;

[0062] acid anhydride curing agent 130 parts to 170 parts;

[0063] polyol 7 parts to 16 parts;

[0064] antioxidant 0.1 part to 5 parts, preferably 0.2 parts to 3 parts;

[0065] ultraviolet absorber 0.1 part to 5 parts, preferably 0.2 parts to 3 parts;

[0066] accelerator 0.1 part to 20 parts, preferably 0.5 to 5 parts;

[0067] catalyst 0.01 part to 10 parts, preferably 0.1 to 2 parts.

[0068] As a specific embodiment of the present application, the accelerator is selected from one or more of imidazole-based accelerators, amine-based accelerators, substituted urea accelerators, phosphine compounds.

[0069] As a specific embodiment of the present application, the imidazole-based accelerator is selected from one or more of 2-ethyl-4-methylimidazole, 2-methylimidazole, undecyl imidazole.

[0070] As a specific embodiment of the present application, the amine-based accelerator is selected from one or more of benzyl dimethylamine, N,N-diethyl aniline, triethylamine, triethanolamine.

[0071] As a specific embodiment of the present application, the substituted urea accelerator is selected from one or more of N-(2-hydroxyphenyl)-N',N'-dimethylurea, N-(4-chlorophenyl)-N',N'-dimethylurea, N-(2-hydroxy-4-nitrophenyl)-N',N'-dimethylurea.

[0072] As a specific embodiment of the present application, the phosphine compound is selected from one or more of triphenylphosphine, triphenylphosphine chloride, triphenylphosphine bromide, tetraphenylphosphine, benzyltriphenylphosphonium bromide, tetrabutyl O,O-diethyl dithiophosphoric acid phosphonium.

[0073] As a specific embodiment of the present application, the catalyst is selected from one of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium methoxide, sodium formate, potassium formate, sodium acetate, potassium acetate, sodium propionate, potassium propionate, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, n-hexylamine, diethylamine, triethylamine, tributylamine, triphenylphosphine, diazabicycloundecene, dicyandiamide, tetraisopropyl titanate, tetrabutyl titanate, titanium acetylacetonate, titanium diisopropoxybis(ethylacetoacetate), triisobutoxyaluminum, triisopropoxyaluminum, aluminum triacetylacetonate, diethylacetylacetonate, aluminum monoacetylacetonate, zirconium tetraacetylacetonate, zirconium tetrabutyrate, cobalt naphthenate, cobalt octoate, cobalt acetylacetonate, iron acetylacetonate, tin acetylacetonate, dimethylhydroxytin oleate, dioctyltin maleate, di-n-butyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, stannous acetate, stannous octoate, zinc octoate, zinc p-t-butylbenzoate, zinc laurate, zinc stearate, zinc dimethylacrylate, zinc benzoate, zinc isooctoate, zirconium isooctoate, aluminum chloride, aluminum perchlorate, aluminum phosphate, aluminum triisopropylate, and aluminum triacetylacetonate.

[0074] In a third aspect, the present application provides an application of the optical chip packaging material provided in the first aspect of the present application or the optical chip packaging material prepared by the preparation method provided in the second aspect of the present application in LED chip packaging.

[0075] In a fourth aspect, the present application provides an LED element, which comprises a substrate, an LED chip, and a molded packaging layer covering the LED chip.

[0076] The molded packaging layer comprises the optical chip packaging material provided in the first aspect of the present application or the optical chip packaging material prepared by the preparation method provided in the second aspect of the present application.

[0077] In a fifth aspect, the present application provides an encapsulation method of an LED chip, which comprises curing the optical chip packaging material on a substrate on which an LED is pasted.

[0078] In the present application, the encapsulation method is a molding curing method, and the curing conditions of the molding curing method comprise curing at 170°C for 4 min and then curing at 150°C for 4 h.

[0079] In the present application, the LED chip is not particularly limited, and a chip known in the art can be used.

[0080] In the present application, the fraction is a weight fraction unless otherwise specified.

[0081] Compared with the prior art, the present application has the following beneficial effects.

[0082] The application can be better reacted with the epoxy resin by modifying the organic silicon resin, so that the optical chip packaging material obtained has enhanced heat-resistant stability and light decay resistance, can significantly reduce the modulus reduction stress, improve the reflow soldering performance of the packaging material, thereby reducing the reflow soldering dead lamp rate and enhancing the product reliability. DETAILED DESCRIPTION

[0083] The application will be further described below in combination with specific examples, but does not constitute any limitation to the application.

[0084] The raw materials used in the embodiments of the application are all from the market, wherein,

[0085] The epoxy resin A1 is isocyanuric acid triglycidyl ester (epoxy equivalent weight 100), Nippon Shokubai Co., Ltd.;

[0086] The epoxy resin A2 is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate, Daiso Corporation;

[0087] The epoxy resin A3 is bisphenol A type epoxy resin (epoxy equivalent weight 550), Dow Chemical Company;

[0088] The acid anhydride curing agent C is methylhexahydrophthalic anhydride (acid anhydride equivalent weight 168), Shin Nippon Rikagaku K.K.;

[0089] The polyhydroxy compound D is neopentyl glycol, TCI;

[0090] The antioxidant E is 2,6-di-tert-butyl-p-cresol, Nanjing Quntong;

[0091] The ultraviolet absorber F is 2-hydroxy-4-methoxybenzophenone, TCI;

[0092] Methyltrimethoxysilane, Jiangxi Chen Guang;

[0093] Phenyltrimethoxysilane, Jiangxi Chen Guang;

[0094] Gamma-glycidoxypropyl methyl dimethoxysilane (silane coupling agent), Wuhan Kanos;

[0095] Monohydroxyl-terminated polydimethylsiloxane with a degree of polymerization n=5-6 (monohydroxyl-terminated silicone oil), Wuhan Slikway Import & Export Co., Ltd.;

[0096] Xylene, Beijing Yili;

[0097] 98wt% H2SO4, Henan Dongke;

[0098] The accelerator G is tetrabutyl O,O-diethylphosphorodithioate phosphine, Japan Chemical Industry Co., Ltd.;

[0099] Catalyst H is zinc isooctoate, Hubei Jusheng Science and Technology.

[0100] According to the weight parts described in Table 1, the epoxy resin, the silicone hybrid resin, the anhydride curing agent, the polyhydroxy compound, the antioxidant and the ultraviolet absorber are mixed to obtain a mixture, the mixture is raised from 25℃ to 130℃ at a rate of 4℃ / min; then reacted at a temperature of 130℃ for 30min; then the temperature is lowered to 70℃ at a rate of 3℃ / min, after adding the accelerator and the catalyst, the reaction is continued for 5h to obtain the optical chip packaging material.

[0101] Table 1

[0102]

[0103] In Table 1, the raw material formula and preparation method of the silicone hybrid resin B1 are as follows:

[0104] Put 890 parts by weight of methyltrimethoxysilane, 760 parts by weight of phenyltrimethoxysilane, 58 parts by weight of γ-glycidoxypropylmethyldimethoxysilane and 300 parts by weight of dimethylbenzene into a reactor, stir at 500 rpm for 20 min to form a first mixture.

[0105] Under the condition that the temperature of the reactor is 30℃, a second mixture composed of 810 parts by weight of deionized water and 1.2 parts by weight of H2SO4 is added dropwise into the reactor. After the second mixture is completely added, the temperature in the reactor is kept at 70℃, and the reactor is kept in a reflux state for 5 hours to obtain a hydrolysis reaction product.

[0106] The hydrolysis reaction product is cooled at 10℃ and allowed to stand for 12h to obtain an organic phase and an aqueous phase, and the organic phase and the aqueous phase are separated, and then the organic phase is transferred to a distillation reactor, the temperature of the reactor is raised to 75℃, and then 60 parts by weight of monohydroxyl-terminated polydimethylsiloxane is added dropwise (added completely within 30min) and stirred at a speed of 500 rpm to carry out a condensation reaction, and the condensation reaction is carried out for 2.5 hours. Then the temperature is raised to 120℃ to remove the remaining solvent and low-boiling substances by reduced pressure distillation to obtain a colorless transparent solid, i.e. the silicone hybrid resin B1.

[0107] The preparation method of the silicone hybrid resin B2 in Table 1 is the same as that of the silicone hybrid resin B1, and the difference is that the raw material formula of the silicone hybrid resin B2 is as follows: 870 parts by weight of methyltrimethoxysilane, 820 parts by weight of phenyltrimethoxysilane, 57 parts by weight of γ-glycidoxypropylmethyldimethoxysilane, 300 parts by weight of dimethylbenzene, and 61 parts by weight of monohydroxyl-terminated polydimethylsiloxane.

[0108] The preparation method of the silicone hybrid resin B3 is the same as that of the silicone hybrid resin B1, except that the raw material formula of the silicone hybrid resin B3 is: 850 parts by weight of methyltrimethoxysilane, 880 parts by weight of phenyltrimethoxysilane, 56 parts by weight of γ-glycidoxypropylmethyldimethoxysilane, 300 parts by weight of dimethylbenzene, and 62 parts by weight of monohydroxyl-terminated polydimethylsiloxane. The second mixed solution is composed of 810 parts by weight of deionized water and 1.5 parts by weight of H2SO4.

[0109] The preparation method of the silicone hybrid resin B4 is the same as that of the silicone hybrid resin B1, except that the raw material formula of the silicone hybrid resin B4 is: 900 parts by weight of methyltrimethoxysilane, 770 parts by weight of phenyltrimethoxysilane, 48 parts by weight of γ-glycidoxypropylmethyldimethoxysilane, 300 parts by weight of dimethylbenzene, and 37 parts by weight of monohydroxyl-terminated polydimethylsiloxane.

[0110] The preparation method of the silicone hybrid resin B5 is the same as that of the silicone hybrid resin B1, except that the raw material formula of the silicone hybrid resin B5 is: 810 parts by weight of methyltrimethoxysilane, 860 parts by weight of phenyltrimethoxysilane, 96 parts by weight of γ-glycidoxypropylmethyldimethoxysilane, 300 parts by weight of dimethylbenzene, and 86 parts by weight of monohydroxyl-terminated polydimethylsiloxane. The second mixed solution is composed of 810 parts by weight of deionized water and 1.5 parts by weight of H2SO4.

[0111] Comparative Examples 1-7

[0112] The comparative examples are used to illustrate the optical chip packaging material and the preparation method thereof.

[0113] The epoxy resin, the silicone hybrid resin, the anhydride curing agent, the polyhydroxy compound, the antioxidant, and the ultraviolet absorber are mixed according to the parts by weight described in Table 2 to obtain a mixture. The mixture is heated from 25°C to 130°C at a heating rate of 4°C / min. Then, the mixture is reacted at 130°C for 30 min. Then, the temperature is decreased to 70°C at a cooling rate of 3°C / min. After the addition of the accelerator and the catalyst, the mixture is continuously reacted for 5 h to obtain the optical chip packaging material.

[0114] Table 2

[0115]

[0116] In Table 2, the preparation method of the silicone hybrid resin B6 is as follows: 880 parts by weight of methyltrimethoxysilane, 540 parts by weight of phenyltrimethoxysilane, 42 parts by weight of γ-glycidoxypropylmethyldimethoxysilane, and 600 parts by weight of dimethylbenzene are placed in a reactor, stirred at 500 r / min for 20 min to form a first mixed solution.

[0117] The second mixture consisting of 900 parts by weight of deionized water and 1.2 parts by weight of H2SO4 was added dropwise to the reactor at a temperature of 30°C. After the second mixture was added dropwise, the temperature in the reactor was maintained at 70°C, and the reactor was kept in a reflux state. The hydrolysis reaction was carried out for 5 hours to obtain a hydrolysis reaction product. The hydrolysis reaction product was cooled at 10°C and allowed to stand for 12 hours to separate into an organic phase and an aqueous phase. The organic phase and the aqueous phase were separated, and then the organic phase was transferred to a distillation reactor. The temperature of the reactor was increased to 75°C, and then 46 parts by weight of monohydroxyl-terminated polydimethylsiloxane was added dropwise (over 30 minutes) while stirring at a rotation speed of 500 rpm to carry out a condensation reaction. The condensation reaction was carried out for 2.5 hours, and then the temperature was increased to 120°C to remove the remaining solvent and low-boiling substances by distillation under reduced pressure to obtain a colorless transparent solid, i.e., the silicone hybrid resin B7.

[0118] In Table 2, the silicone hybrid resin B7 was prepared by placing 570 parts by weight of methyltrimethoxysilane, 750 parts by weight of phenyltrimethoxysilane, 37 parts by weight of γ-glycidoxypropylmethyldimethoxysilane, and 600 parts by weight of xylene in a reactor, stirring at 500 rpm for 20 minutes, and forming a first mixture.

[0119] The second mixture consisting of 900 parts by weight of deionized water and 1.2 parts by weight of H2SO4 was added dropwise to the reactor at a temperature of 30°C. After the second mixture was added dropwise, the temperature in the reactor was maintained at 70°C, and the reactor was kept in a reflux state. The hydrolysis reaction was carried out for 5 hours to obtain a hydrolysis reaction product.

[0120] The hydrolysis reaction product was cooled at 10°C and allowed to stand for 12 hours to separate into an organic phase and an aqueous phase. The organic phase and the aqueous phase were separated, and then the organic phase was transferred to a reactor. The temperature of the reactor was increased to 75°C, and then 46 parts by weight of monohydroxyl-terminated polydimethylsiloxane was added dropwise (over 30 minutes) while stirring at a rotation speed of 500 rpm to carry out a condensation reaction. The condensation reaction was carried out for 2.5 hours, and then the temperature was increased to 120°C to remove the remaining solvent and low-boiling substances by distillation under reduced pressure to obtain a colorless transparent solid, i.e., the silicone hybrid resin B7.

[0121] In Table 2, the organic silicon resin B8 is prepared as follows: 880 parts by weight of methyltrimethoxysilane, 540 parts by weight of phenyltrimethoxysilane, 42 parts by weight of γ-glycidoxypropylmethyldimethoxysilane and 600 parts by weight of xylene are placed in a reactor, stirred at 500 rpm for 20 min to form a first mixture. At a reactor temperature of 30°C, a second mixture composed of 810 parts by weight of deionized water and 1.2 parts by weight of H2SO4 is added dropwise into the reactor; after the second mixture is completely added, the reactor temperature is kept at 70°C, and the reactor is kept in a reflux state, and the hydrolysis reaction is carried out for 5 hours to obtain a hydrolysis reaction product; the hydrolysis reaction product is cooled at 10°C and allowed to stand for 12 h to separate the organic phase and the aqueous phase, and then the organic phase is transferred to a distillation reactor, the temperature of the distillation reactor is gradually increased to 75°C, and the condensation reaction is carried out by stirring at 500 rpm, and the condensation reaction is carried out for 2.5 hours, and then the temperature is increased to 120°C, and the remaining solvent and low-boiling substances are removed by reduced pressure distillation to obtain a colorless transparent solid, i.e. the organic silicon resin B8.

[0122] In Table 2, B9 is a methylphenyl silicone resin KR 300, Shin-Etsu Chemical.

[0123] To further illustrate the progressiveness of the present application, the light decay resistance and the reflow solder dead lamp resistance of the optical chip packaging materials prepared in Examples 1-10 and Comparative Examples 1-7 are measured and evaluated by the following method:

[0124] (I) Transparency

[0125] The optical chip packaging materials prepared in the examples and comparative examples are respectively made into a cured product test block, and the size of the test block is 2 mm x 30 mm x 30 mm (the curing conditions are: first curing at 170°C for 4 min, and then curing at 150°C for 4 h); whether the appearance of the test block is transparent is observed, and the results are shown in Table 3.

[0126] (II) Light decay resistance at 25°C

[0127] The optical chip packaging materials prepared in the examples and comparative examples are encapsulated LED chips by high-temperature molding curing (curing at 170°C for 4 min, and then curing at 150°C for 4 h) to obtain 0603 patch LED lamp beads. The LED lamp beads are clamped on a patch aging tester (AN208C, Shenzhen Annuode Technology Co., Ltd.), and the light intensity maintenance rate at 500 h and 1000 h is tested and recorded under the condition of 10 mA current lighting at 25°C, and the results are shown in Table 3.

[0128] The light intensity maintenance rate was tested and calculated at 25°C using a high-precision rapid spectral radiometer (HAAS-2000, Hangzhou Yuanfang Optoelectronic Information Co., Ltd.).

[0129] (Three) Light decay resistance at 85°C

[0130] The optical chip packaging materials prepared in the examples and comparative examples were used to package LED chips by high-temperature molding and curing (curing at 170°C for 4 min, and then curing at 150°C for 4 h) to obtain 0603 patch LED lamp beads. The LED lamp beads were clamped on a patch aging tester (AN207B, Shenzhen Annuod Technology Co., Ltd.), and placed in an 85°C oven, and lit at a current of 10 mA. The light intensity maintenance rate at 500 h and 1000 h was tested and recorded, and the results are shown in Table 3.

[0131] The light intensity maintenance rate was tested and calculated at 25°C using a high-precision rapid spectral radiometer (HAAS-2000, Hangzhou Yuanfang Optoelectronic Information Co., Ltd.).

[0132] (Four) UV aging resistance

[0133] The optical chip packaging materials prepared in the examples and comparative examples were used to package LED chips by high-temperature molding and curing (curing at 170°C for 4 min, and then curing at 150°C for 4 h) to obtain 0603 patch LED lamp beads. The LED lamp beads were clamped on a patch aging tester (AN207B, Shenzhen Annuod Technology Co., Ltd.), and placed in an 85°C oven, and lit at a current of 10 mA. The light intensity maintenance rate at 500 h and 1000 h was tested and recorded, and the results are shown in Table 3. 2 The light intensity maintenance rate was tested and calculated at 25°C using a high-precision rapid spectral radiometer (HAAS-2000, Hangzhou Yuanfang Optoelectronic Information Co., Ltd.).

[0134] The light intensity maintenance rate was tested and calculated at 25°C using a high-precision rapid spectral radiometer (HAAS-2000, Hangzhou Yuanfang Optoelectronic Information Co., Ltd.).

[0135] (Five) Flexural modulus and flexural strength at room temperature

[0136] The partially cured resin compositions prepared in Examples 1-10 were each made into one cured product test block with a size of 2mm x 3mm x 40mm (the curing conditions were: first curing at 170°C for 4min, and then curing at 150°C for 4h); and the plastic three-point bending test was performed according to the requirements of ISO 178-2010, JIS K 7171-2016 plastic three-point bending test standard, using the control method of cross head (crossbeam) displacement speed. The test blocks were each measured for the bending elastic modulus and bending strength at room temperature (25°C) using a universal testing machine (INSTRON, LEGEND 2367) with a bending span of 32mm and a loading test rate of 1mm / min.

[0137] (VI) Reflow soldering dead light resistance performance:

[0138] The optical chip packaging materials prepared in Examples 1-10 and Comparative Examples 1-7 were used to package LED chips by high-temperature mold curing (curing at 170°C for 4min, and then curing at 150°C for 4h) to obtain 0603 patch LED lamp beads. The lamp beads were first subjected to moisture absorption at 60°C / 60%RH for 168h, and then were placed in an instrument six-temperature-zone reflow soldering machine (Boluo Jingdian, SMT-H6) for three cycles of testing: the peak temperature was 260±5°C, each cycle took 11min, and the interval between two tests was no more than 10min. After the three cycles, the number of dead light lamp beads was observed and quantitatively calculated, and the results are shown in Table 3.

[0139] Table 3

[0140]

[0141] The performance data in Table 3 above show that the optical chip packaging material obtained by the reaction of the organic silicone hybrid resin and the epoxy composition can significantly improve the light decay resistance, low stress, and reflow soldering dead light resistance of the LED chip packaging product.

[0142] It should be noted that the above-described examples are only used to explain the present application and do not constitute any limitation on the present application. The present application has been described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. The present application can be modified within the scope of the claims, and the present application can be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and examples, it does not mean that the present application is limited to the specific examples disclosed therein, on the contrary, the present application can be extended to all other methods and applications with the same function.

Claims

1. An optical chip package material, characterized by, The optical chip packaging material comprises, by weight fraction, 50-800 parts of epoxy resin, 10-500 parts of organic silicon hybrid resin, 130-185 parts of anhydride curing agent, and 5-20 parts of polyhydroxy compound. The preparation method of the organic silicon hybrid resin comprises: (1) mixing methyltrimethoxysilane, phenyltrimethoxysilane and silane coupling agent with an organic solvent to form a first mixed solution; (2) mixing the first mixed solution with an inorganic acid solution to perform hydrolysis reaction at a temperature of 68-78℃ to obtain a hydrolysis reaction product; (3) separating the hydrolysis reaction product into organic phase and aqueous phase; mixing the organic phase with monohydroxyl-terminated silicone oil at 70-90℃ to perform condensation reaction; removing residual solvent and low-boiling substances by reduced pressure distillation to obtain the organic silicon hybrid resin; the number of carbon atoms of the alkoxy group in the methyltrialkoxysilane is 1-4; the number of carbon atoms of the alkoxy group in the phenyltrialkoxysilane is 1-4; The raw materials for preparing the organic silicon hybrid resin comprise, by weight fraction, 800-910 parts of methyltrialkoxysilane, 700-900 parts of phenyltrialkoxysilane, 50-100 parts of silane coupling agent, and 50-90 parts of monohydroxyl-terminated silicone oil. The silane coupling agent is selected from γ-glycidyloxypropylmethyldimethoxysilane or β(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The epoxy resin is selected from one or more of glycidyl ester type epoxy resin, glycidyl ether type epoxy resin, glycidyl amine type epoxy resin and alicyclic epoxy resin.

2. The optical chip package material of claim 1, wherein, The optical chip packaging material comprises, by weight fraction, epoxy resin 100-550 parts; organic silicon hybrid resin 30-400 parts; anhydride curing agent 130-170 parts; polyhydroxy compound 7-16 parts; antioxidant 0.1-5 parts; ultraviolet absorber 0.1-5 parts.

3. The optical chip package material according to claim 1 or 2, characterized in that, The molecular formula of the monohydroxyl-terminated silicone oil is shown in formula (1): Equation (1), In formula (1), R 1 , R 2 are each independently selected from C1-C6 monovalent alkyl groups; n is a natural number of 3-8.

4. The optical chip packaging material according to claim 2, wherein the epoxy resin is selected from any one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; and / or, the anhydride curing agent is selected from one or more of phthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, maleic anhydride, pyromellitic anhydride, trimellitic anhydride, glutaric anhydride, tung oil anhydride, hexachloroendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, 1,2,3,4-cyclopentane tetra carboxylic dianhydride and methylcyclohexene tetra carboxylic dianhydride; and / or, the polyhydroxy compound is selected from one or more of polyhydric alcohol.

5. The optical chip packaging material according to claim 4, wherein the polyhydroxy compound is selected from one or more of polyester polyhydric alcohol or polyether polyhydric alcohol; and / or, the antioxidant is selected from one or more of ammonia compound, phosphorus compound, organic sulfur compound and phenol compound. And / or, the ultraviolet absorber is selected from one or several of hindered amine ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers.

6. A method of producing the optical chip package material according to any one of claims 1 to 5, characterized by, The optical chip packaging material is prepared by mixing an epoxy resin, a silicone hybrid resin, an acid anhydride curing agent and a polyhydroxy compound.

7. The preparation method according to claim 6, characterized in that, The mixing reaction comprises the following steps: (1) mixing the epoxy resin, the silicone hybrid resin, the acid anhydride curing agent, the polyhydroxy compound, an antioxidant and an ultraviolet absorber, and reacting at 90-150°C for 10-60 minutes; (2) adding an accelerator and a catalyst, and continuing to react at 60-80°C for 1-12 hours to obtain the optical chip packaging material.

8. Use of the optical chip packaging material of any one of claims 1-5 or the optical chip packaging material prepared by the preparation method of any one of claims 6-7 in LED chip packaging.

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