Flame-retardant and light-transmitting LED packaging adhesive and preparation method thereof

Abstract

The invention provides an LED packaging adhesive, a preparation method and an LED packaging method, and belongs to the technical field of LED chip packaging. The LED packaging adhesive comprises the following raw materials: a component A and a component B, the component A comprises epoxy resin; the component B comprises a curing agent and a curing accelerator; the component A and / or the component B contain a compound as shown in a formula I: # imgabs0 #, R1 and R2 are organic groups, n is greater than or equal to 3, and n is an integer. The flame retardance of the prepared LED packaging adhesive can reach UL-94V-0 level, the LOI value can reach 33%-37%, and the brightness of LED lamp beads is not affected.

Description

Technical Field

[0001] The invention relates to the technical field of LED chip packaging, and in particular to a flame retardant and light-transmitting packaging adhesive and a preparation method thereof. Background Art

[0002] LED (Light Emitting Diode) is a new type of solid light source in the 21st century. Compared with traditional light sources, it has the advantages of energy saving, environmental protection, low cost, easy maintenance, safety and reliability. With the development of the times, higher requirements are put forward for the power, brightness and fire safety of LED lighting equipment.

[0003] The main function of packaging materials is to protect the LED chip from corrosion by water vapor and chemical gases in the air. Currently, epoxy resin packaging glue with excellent moisture resistance and air tightness is one of the main products for outdoor LED packaging. However, epoxy resin is very flammable. Once ignited, the flame spreads quickly and releases a lot of heat and toxic and harmful smoke, so it needs to be flame-retardant modified.

[0004] Halogen flame retardants will release toxic and corrosive gases during the flame retardant process, which is harmful to human health. The European Union has banned the use of halogenated flame retardants in all electronic display screens and displays in 2021. In addition, the flame retardant methods currently used in epoxy resins often lead to the deterioration of optical properties and heat resistance / UV yellowing properties, which greatly limits the application of flame retardant epoxy resins in LED packaging. Therefore, how to obtain epoxy resins that have halogen-free flame retardancy, optical properties and reliability to meet the needs of LED use has great research and application value. If the LED packaging material has good flame retardant properties, it can effectively reduce the fire hazard of the encapsulated epoxy resin and reduce personal and property losses. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a flame retardant and light-transmitting encapsulant and a preparation method and application thereof.

[0006] In one aspect, the present invention provides an LED encapsulation adhesive, wherein the raw materials of the LED encapsulation adhesive include component A and component B; the component A includes epoxy resin; the component B includes a curing agent and a curing accelerator; the component A and / or the component B contains a compound represented by formula I:

[0007]

[0008] Wherein, R1 and R2 are organic groups, each independently selected from substituted or unsubstituted aryl, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted C 1-10 Alkoxy, substituted or unsubstituted amine, n≥2, n is an integer.

[0009] The aryl group is preferably a phenyl group.

[0010] The C 1-10 The alkyl group is preferably a methyl group, a deuterated methyl group, an ethyl group or a tert-butyl group.

[0011] The aryloxy group is preferably a phenoxy group.

[0012] The C 1-10 The alkoxy group is preferably a methoxy group, an ethoxy group or a propoxy group.

[0013] The amino group is preferably an amino group, a methylamino group, or an ethylamino group.

[0014] As a preferred technical solution, the substituted or unsubstituted aryl group has a substituent I, and the substituent I is selected from a hydrogen atom, a deuterium atom, a C 1-10 Any of alkyl, cyano, acyl, amino, nitroso, nitro and hydroxy.

[0015] As a preferred technical solution, the substituted or unsubstituted C 1-10 The alkyl group has a substituent II, and the substituent II is selected from any one of a hydrogen atom, a deuterium atom, a cyano group, an acyl group, an amino group, a nitroso group, a nitro group, a hydroxyl group, and a phenoxy group.

[0016] As a preferred technical solution, the substituted or unsubstituted aryloxy group has a substituent III, and the substituent III is selected from a hydrogen atom, a deuterium atom, a C 1-10 Any of alkyl, cyano, acyl, amino, nitroso, nitro and hydroxy.

[0017] As a preferred technical solution, the substituted or unsubstituted C 1-10 The alkoxy group has a substituent IV, and the substituent IV is selected from any one of a hydrogen atom, a deuterium atom, a cyano group, an acyl group, an amino group, a nitroso group, a nitro group, a hydroxyl group, and a phenoxy group.

[0018] As a preferred technical solution, the substituted or unsubstituted C 1-10 The alkoxy group has a substituent V, and the substituent IV is selected from a hydrogen atom, a C 1-10 Any of an alkyl group and a phenyl group.

[0019] Optionally, the weight ratio of component A to component B is 100:(0.1-200).

[0020] Optionally, in the component B, the ratio of the curing agent to the curing agent accelerator is 100:0.1-20, preferably 100:(1-5).

[0021] The compound represented by formula I of the present invention is a phosphazene compound.

[0022] The present invention finds that among epoxy resin flame retardants, phosphazene compounds have both the acid source and gas source of the intumescent flame retardant, are halogen-free, have high flame retardant efficiency, require a small amount of addition, have good thermal stability, can form a colorless and transparent cured product with epoxy resin, and do not affect the adhesion of the epoxy resin.

[0023] As a preferred technical solution, in the raw materials of the LED packaging glue, the phosphazene compound accounts for 5% to 50% of the total mass of the raw materials; preferably 10% to 30%.

[0024] As a preferred technical solution, the phosphazene compound is selected from one or more of cyclophosphazene and linear polyphosphazene; when the phosphazene compound is cyclophosphazene, n=3-8; when the phosphazene compound is linear polyphosphazene, n≥2.

[0025] As a preferred technical solution, the cyclophosphazene is selected from one or more of phenoxy cyclotriphosphazene, tris(o-phenylenedioxy) cyclophosphazene, hexamethoxy cyclotriphosphazene, hexa(deuterated methyl) cyclotriphosphazene, hexa(4-tert-butylphenoxy) cyclotriphosphazene, hexa(4-methylphenoxy) cyclotriphosphazene, hexa(p-aminophenoxy) cyclotriphosphazene, hexa(p-nitrophenoxy)-cyclotriphosphazene, hexa(4-carboxyphenoxy) cyclotriphosphazene, hexaaminocyclotriphosphazene, hexa(3,5-dicarboxyphenoxy) cyclotriphosphazene, and cyclotriphosphazene-PMMH-6 polymer.

[0026] As a preferred technical solution, the linear polyphosphazene is selected from hexaphenyltriphosphazene, poly(4-nitrophenoxy)phosphazene, phenoxy polyphosphazene, poly(di(methoxy)phosphazene), polybis(methoxyethoxyethoxy)phosphazene, ethoxy polyphosphazene, propoxy polyphosphazene, cyclobutoxy polyphosphazene, cyclopentyloxy polyphosphazene, ethylamino polyphosphazene, propylamino polyphosphazene, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2Λ5,4Λ5-bis(phosphorus nitrogen-based compound), poly[bis(alkoxy)(aryloxy)phosphazene], poly[bis(1-(ethoxycarbonyl)-2-phenylethylamino)phosphazene], 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2Λ5,4Λ5-bis(phosphorus nitrogen-based compound) and one or more thereof.

[0027] As a preferred technical solution, the epoxy resin is selected from one or more of glycidyl ester epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin and alicyclic epoxy resin.

[0028] According to some embodiments of the present invention, the epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, 2,3-epoxypropyl acrylate, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexanemethyl ester, 3,4-epoxy-6-methylcyclohexanecarboxylic acid-3',4'-epoxy-6'-methylcyclohexanemethyl ester. Ester, triglycidyl triisocyanate, triglycidyl p-aminophenol, tetraglycidyl diaminodiphenylmethane, tetramethylisopropylphenylene tetraglycidylamine, N,N,N',N'-tetraepoxypropyl-4,4-diaminodiphenylmethane, N,N,N",N-tetraglycidyl-4,4'-methylenedi-o-toluidine, 4,4-diaminodiphenyl ether tetraglycidylamine, diaminodiphenylmethane tetraglycidylamine, bicyclo Pentadiene diepoxy, cis-bis-(2,3-epoxycyclopentyl)-ether, trans-bis-(2,3-epoxycyclopentyl)-ether, 3,4-epoxycyclohexylmethyl-2',3'-epoxycyclohexyl ether, 2,2-bis(3,3"-epoxycyclohexyl)propane, bis-(2,3-epoxycyclohexane), 1,2-bis-(2,3-epoxycyclohexyloxy)-ethane, bis-(2,3-epoxycyclohexyl) ether, 1,1- One or more of bis(2',3'-epoxycyclohexyloxymethyl)-3,4-epoxycyclohexane, 2,2'-((propane-2,2-diylbis(4,1-phenylene))bis(methylene))bis(ethylene oxide), ethylene glycol glycidyl ether, 1,4-butanediol diglycidyl ether, resorcinol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and neopentyl glycol diglycidyl ether.

[0029] Preferably, the glycidyl ester epoxy resin is selected from at least one of diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl terephthalate, diglycidyl isophthalate, diglycidyl tetrahydrophthalate, diglycidyl methyltetrahydrophthalate, diglycidyl endomethyltetrahydrophthalate, diglycidyl adipate and 2,3-epoxypropyl acrylate;

[0030] Preferably, the glycidylamine epoxy resin is selected from at least one of triglycidyl triisocyanate, triglycidyl p-aminophenol, tetraglycidyl diaminodiphenylmethane, tetramethylisopropylphenylene tetraglycidylamine, N,N,N',N'-tetraepoxypropyl-4,4-diaminodiphenylmethane, N,N,N",N-tetraglycidyl-4,4'-methylenedi-o-toluidine, 4,4-diaminodiphenyl ether tetraglycidylamine and diaminodiphenylmethane tetraglycidylamine;

[0031] The glycidyl ether epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, dicyclopentadiene diepoxy, 3,4-epoxycyclohexylmethyl-2',3'-epoxycyclohexyl ether, ethylene glycol glycidyl ether, 1,4-butanediol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether and 2,2'-((propane-2,2-diylbis(4,1-phenylene))bis(methylene))bis(ethylene oxide).

[0032] The alicyclic epoxy resin is selected from bis(3,4-epoxycyclohexylmethyl)adipate, 3',4'-epoxycyclohexanemethyl 3,4-epoxycyclohexanecarboxylate, 3',4'-epoxy-6'-methylcyclohexanemethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, 2,2-bis(3,3"-epoxycyclohexyl)propane, bis-(2,3-epoxycyclohexane), 1,2 - at least one of bis-(2,3-epoxycyclohexyloxy)-ethane, bis-(2,3-epoxycyclohexyl) ether, 1,1-bis(2',3'-epoxycyclohexyloxymethyl)-3,4-epoxycyclohexane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, cis-bis-(2,3-epoxycyclopentyl)-ether and trans-bis-(2,3-epoxycyclopentyl)-ether.

[0033] As a preferred technical solution, the curing agent is selected from at least one of amine curing agents, anhydride curing agents, polyamide resins, phenolic resins, imidazole curing agents, boron trifluoride-amine complexes, and cationic curing agents; preferably, the relative molecular mass of the polyamide resin is less than 10,000.

[0034] According to some embodiments of the present invention, the curing agent is selected from diethylenetriamine, tetramethylenepentamine, hexamethylenediamine, diethylaminopropylamine, meta-xylene diamine, meta-phenylenediamine, dicyandiamide, N-aminoethylpiperazine, 1,3-bis(aminomethyl)cyclohexane, bismaleimide, diazinone, 2-methylimidazole, 2-ethyl-2-methylimidazole, phthalic anhydride, methylhexahydrophthalic anhydride, dodecylsuccinic anhydride, polyazetadine anhydride, polylaurolactam, polyhexamethylene adipamide, polyamide 651, polyamide 650, linear phenolic resin, bisphenol A-based phenolic resin, boron trifluoride monoethylamine, boron trifluoride aniline, triarylsulfonium salt, triarylsulfonium hexafluorophosphate, diaryliodonium salt, bis(4-tert-butylphenyl)iodonium tetraphenylborate or more.

[0035] Preferably, the amine curing agent is selected from at least one of diethylenetriamine, tetramethylenepentamine, hexamethylenediamine, diethylaminopropylamine, meta-xylene diamine, meta-phenylenediamine, dicyandiamide, 1-piperazineethylamine, bismaleimide and phthalazinone;

[0036] Preferably, the acid anhydride curing agent is selected from at least one of phthalic anhydride, methylhexahydrophthalic anhydride, dodecylsuccinic anhydride and polyazelaic anhydride;

[0037] Preferably, the polyamide resin is selected from at least one of polylaurolactam, polyhexamethylene adipamide, polyamide 651 and polyamide 650;

[0038] Preferably, the phenolic resin is selected from at least one of bisphenol A-based phenolic resin and novolac resin;

[0039] Preferably, the imidazole curing agent is selected from at least one of 2-methylimidazole and 2-ethyl-4,2-methylimidazole;

[0040] Preferably, the boron trifluoride-amine complex is selected from at least one of boron trifluoride monoethylamine and boron trifluoride aniline;

[0041] Preferably, the cationic curing agent is at least one selected from triarylsulfonium salts, triarylsulfonium hexafluorophosphates, diaryliodonium salts and bis(4-tert-butylphenyl)iodonium tetraphenylborate.

[0042] As a preferred technical solution, the curing accelerator is selected from one or more of substituted urea, metal salt of acetylacetonate, metal salt of carboxylate and its complex, quaternary ammonium salt, thiourea and its derivatives, organic guanidine, organic phosphine and peroxide.

[0043] According to some embodiments of the present invention, the curing accelerator is selected from one or more of N-(4-chlorophenyl)dimethylurea, zinc acetylacetonate, copper acetylacetonate, neodymium acetylacetonate, aluminum acetylacetonate, zinc naphthenate, cobalt naphthenate, manganese naphthenate, zinc isooctanoate, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetraethylammonium hydroxide, thiourea, ethylenethiourea, allylthiourea, tetramethylguanidine, triphenylphosphine, tetraphenylphosphine bromide, tetrabutylphosphine acetate, benzoyl peroxide, di-tert-butyl peroxide, and tert-butyl peroxybenzoate.

[0044] Preferably, the substituted urea is selected from N-(4-chlorophenyl)dimethylurea;

[0045] Preferably, the acetylacetonate metal salt is selected from at least one of zinc acetylacetonate, copper acetylacetonate, neodymium acetylacetonate and aluminum acetylacetonate;

[0046] Preferably, the thiourea and its derivatives are selected from at least one of thiourea, ethylenethiourea and allylthiourea;

[0047] Preferably, the peroxide is selected from at least one of di-tert-butyl peroxide, tert-butyl peroxybenzoate and benzoyl peroxide;

[0048] Preferably, the organic guanidine is selected from tetramethylguanidine;

[0049] Preferably, the organic phosphine is selected from at least one of triphenylphosphine, tetraphenylphosphine bromide and tetrabutylphosphonium acetate;

[0050] Preferably, the carboxylic acid metal salt and its complex are selected from at least one of zinc naphthenate, cobalt naphthenate, manganese naphthenate and zinc isooctanoate;

[0051] Preferably, the quaternary ammonium salt is selected from at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide and tetraethylammonium hydroxide.

[0052] As a preferred technical solution, the flame retardancy of the LED encapsulation adhesive is UL-94V-0 level, the LOI value is 32% to 37%, the strip size is 125mm*13mm*5mm, and it does not affect the brightness of the LED lamp beads.

[0053] On the other hand, the present invention provides a method for preparing any of the above-mentioned LED packaging adhesives, mixing the component A and the component B at room temperature to obtain the LED packaging adhesive, wherein in component A, the epoxy resin and the phosphazene compound are mixed at 60 to 100° C., preferably 80° C., and mixed until they are uniform and transparent; in component B, the curing agent, the curing accelerator and the phosphazene are mixed at 60 to 100° C., preferably 80° C., and mixed until they are uniform and transparent.

[0054] The flame retardancy of the LED encapsulation adhesive prepared by the invention can reach UL-94V-0 level, the LOI value can reach 32%-37%, and the brightness of the LED lamp beads is not affected. DETAILED DESCRIPTION

[0055] The present invention will be further described below in conjunction with the embodiments, but they do not constitute any limitation to the present invention.

[0056] The raw materials used in the embodiments of the present invention are commercially available: 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester was purchased from Sinopharm Reagent, CAS No.: 2386-87-0;

[0057] Resorcinol diglycidyl ether was purchased from Sinopharm Reagent, CAS No.: 101-90-6;

[0058] Methylhexahydrophthalic anhydride was purchased from Sinopharm Reagent, CAS No.: 25550-51-0;

[0059] Diethylenetriamine was purchased from Sinopharm Reagent, CAS No.: 111-40-0;

[0060] 2-Methylimidazole was purchased from Sinopharm Reagent, CAS No.: 693-98-1;

[0061] Triphenylphosphine was purchased from Sinopharm Reagent, CAS No.: 603-35-0;

[0062] Hexaphenyltriphosphazene was purchased from Sinopharm Reagent, CAS No.: 1110-78-7;

[0063] Phenoxy cyclophosphazene was purchased from Sinopharm Reagent, CAS No.: 1184-10-7;

[0064] Hexamethoxycyclotriphosphazene was purchased from Sinopharm Reagent, CAS No.: 957-13-1;

[0065] Hexa(deuterated methyl)cyclotriphosphazene was purchased from Sinopharm Reagent, CAS No.: 105809-15-2;

[0066] 1-tert-Butyl-2,2,4,4,4-penta(dimethylamino)-2Λ5,4Λ5-di(phosphinogen-based compound) was purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd., CAS No.: 111324-03-9.

[0067] Example 1 Preparation of LED packaging glue and use for LED lamp bead packaging

[0068] Preparation of component A: 100 parts of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 30 parts of phenoxy cyclophosphazene were mixed, stirred at 80° C. for 1 h until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0069] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of 2-methylimidazole were mixed, stirred at 80° C. for 1 hour until the mixture was uniform and transparent, and then allowed to cool to room temperature.

[0070] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japan Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130°C for 1h, then heated at 150°C for 4h, and cooled to room temperature to obtain packaged lamp bead 1# encapsulated with LED packaging glue.

[0071] Example 2 Preparation of LED packaging glue and use for LED lamp bead packaging

[0072] Preparation of component A: 100 parts of resorcinol diglycidyl ether and 30 parts of phenoxy cyclophosphazene were mixed, stirred at 80° C. for 1 hour until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0073] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of 2-methylimidazole were mixed and stirred at 80° C. for 1 hour until the mixture was homogeneous and transparent, and then allowed to stand at room temperature.

[0074] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japan Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130°C for 1h, then heated at 150°C for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 2# encapsulated with LED encapsulation glue.

[0075] Example 3 Preparation of LED packaging glue and use for LED lamp bead packaging

[0076] Preparation of component A: 100 parts of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 30 parts of hexaphenyl triphosphazene were mixed, stirred at 80° C. for 1 hour until the mixture was uniform and transparent, and then allowed to cool to room temperature.

[0077] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of 2-methylimidazole were mixed, stirred at 80° C. for 1 hour until the mixture was uniform and transparent, and then allowed to cool to room temperature.

[0078] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japan Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130℃ for 1h, then heated at 150℃ for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 3# encapsulated with encapsulation glue.

[0079] Example 4 Preparation of LED packaging glue and use for LED lamp bead packaging

[0080] Preparation of component A: 100 parts of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 30 parts of hexamethoxycyclotriphosphazene were mixed, stirred at 80° C. for 1 h until the mixture was uniform and transparent, and then allowed to cool to room temperature.

[0081] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of 2-methylimidazole were mixed, stirred at 80° C. for 1 hour until the mixture was uniform and transparent, and then allowed to cool to room temperature.

[0082] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japan Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130℃ for 1h, then heated at 150℃ for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 4# encapsulated with encapsulation glue.

[0083] Example 5 Preparation of LED packaging glue and use for LED lamp bead packaging

[0084] Preparation of component A: 100 parts of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 30 parts of hexa(deuterated methyl)cyclotriphosphazene were mixed, stirred at 80° C. for 1 h until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0085] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of 2-methylimidazole were mixed, stirred at 80° C. for 1 hour until the mixture was uniform and transparent, and then allowed to cool to room temperature.

[0086] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japan Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130℃ for 1h, then heated at 150℃ for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 5# encapsulated with encapsulation glue.

[0087] Example 6 Preparation of LED packaging glue and use for LED lamp bead packaging

[0088] Preparation of component A: Mix 100 parts of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 30 parts of 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2Λ5,4Λ5-di(phosphorus nitrogen compound), stir at 80° C. for 1 h until the mixture becomes a uniform, transparent homogeneous state, and then allow to cool to room temperature.

[0089] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of 2-methylimidazole were mixed, stirred at 80° C. for 1 hour until the mixture was uniform and transparent, and then allowed to cool to room temperature.

[0090] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japan Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130℃ for 1h, then heated at 150℃ for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 6# encapsulated with encapsulation glue.

[0091] Example 7 Preparation of LED packaging glue and use for LED lamp bead packaging

[0092] Preparation of component A: 100 parts of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 30 parts of phenoxy cyclophosphazene were mixed, stirred at 80° C. for 1 h until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0093] Preparation of component B: 100 parts of diethylenetriamine and 3 parts of 2-methylimidazole were mixed, stirred at 80° C. for 1 hour until the mixture was in a transparent homogeneous state, and then allowed to cool to room temperature.

[0094] Component A and component B were mixed evenly in a weight ratio of A:B=100:30 to remove bubbles, and then glue was dispensed (using Japanese Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130°C for 1h, then heated at 150°C for 4h, and cooled to room temperature to obtain LED encapsulated lamp bead 7# encapsulated with encapsulation glue.

[0095] Example 8 Preparation of LED packaging glue and use for LED lamp bead packaging

[0096] Preparation of component A: 100 parts of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 30 parts of phenoxy cyclophosphazene were mixed, stirred at 80° C. for 1 h until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0097] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of triphenylphosphine were mixed at 80° C. and stirred for 1 hour until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0098] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japanese Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130℃ for 1h, then heated at 150℃ for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 8# encapsulated with encapsulation glue.

[0099] Example 9: Preparation of LED packaging glue and use for LED lamp bead packaging

[0100] Preparation of component A: 100 parts of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 30 parts of phenoxy cyclophosphazene were mixed, stirred at 80° C. for 1 h until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0101] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of 2-methylimidazole were mixed, stirred at 80° C. for 1 hour until the mixture was uniform and transparent, and then allowed to cool to room temperature.

[0102] After mixing component A and component B in a weight ratio of A:B=100:120 to remove bubbles, glue was dispensed (using Japan Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130℃ for 1h, then heated at 150℃ for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 9# encapsulated with encapsulation glue.

[0103] Example 10 Preparation of LED packaging glue and use for LED lamp bead packaging

[0104] Preparation of component A: 100 parts of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 50 parts of phenoxy cyclophosphazene were mixed, stirred at 80° C. for 1 h until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0105] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of 2-methylimidazole were mixed, stirred at 80° C. for 1 hour until the mixture was uniform and transparent, and then allowed to cool to room temperature.

[0106] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japanese Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130℃ for 1h, then heated at 150℃ for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 10# encapsulated with encapsulation glue.

[0107] Example 11 Preparation of LED packaging glue and use for LED lamp bead packaging

[0108] Component A: 100 parts of 3',4'-epoxycyclohexanemethyl 3,4-epoxycyclohexanecarboxylate.

[0109] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride, 3 parts of 2-methylimidazole and 30 parts of phenoxy cyclophosphazene were mixed, stirred at 80° C. for 1 h until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0110] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japan Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130℃ for 1h, then heated at 150℃ for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 11# encapsulated with encapsulation glue.

[0111] Comparative Example 1: Preparation of LED encapsulation glue and use for LED lamp bead encapsulation

[0112] Component A: 100 parts of 3',4'-epoxycyclohexanemethyl 3,4-epoxycyclohexanecarboxylate.

[0113] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of 2-methylimidazole were mixed and stirred at 80° C. for 1 hour until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0114] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japan Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130℃ for 1h, then heated at 150℃ for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 12# encapsulated with LED encapsulation glue.

[0115] Comparative Example 2: Preparation of LED encapsulation glue and use for LED lamp bead encapsulation

[0116] Preparation of component A: 100 parts of 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexane methyl ester and 30 parts of ammonium polyphosphate were mixed, stirred at 80° C. for 1 hour until the mixture was uniform and transparent, and then allowed to cool to room temperature.

[0117] Preparation of component B: 100 parts of methylhexahydrophthalic anhydride and 3 parts of 2-methylimidazole were mixed and stirred at 80° C. for 1 hour until the mixture was homogeneous and transparent, and then allowed to cool to room temperature.

[0118] After mixing component A and component B in a weight ratio of A:B=100:90 to remove bubbles, glue was dispensed (using Japan Musashi, shotmaster300 glue dispenser) on the lamp bead, heated at 130℃ for 1h, then heated at 150℃ for 4h, cooled to room temperature, and obtained LED encapsulated lamp bead 13# encapsulated with encapsulation glue.

[0119] Test Example 1 Brightness Test

[0120] The LED light, color and electricity testing system was used to test the brightness of the packaged lamp beads obtained in Examples 1 to 8 and Comparative Examples 1 to 2 (100 each, each example and comparative example used blue light lamp beads of model 3528) at a current of 20 mA. The experimental results are shown in Table 1.

[0121] Test Example 2 Flame retardant performance test

[0122] The encapsulation glue of implementation cases 1 to 8 and comparative examples 1 to 2 was cured into 10mm*4mm*100mm specimens, respectively, and the UL-94 grade and oxygen index were tested in accordance with "GB / T 2408-2021 Determination of combustion performance of plastics" and "GB T 2406.2-2009 Determination of combustion behavior of plastics by oxygen index method". The experimental results are shown in Table 1.

[0123] Test Example 3: Reliability Test

[0124] The packaged lamp beads of implementation cases 1 to 8 and comparative examples 1 to 2 were placed in a box at 85°C and 85% humidity for 24 hours. After being taken out, they were heat treated at 250°C / 10 min respectively to observe the interface peeling between the LED lamp bead bracket and the packaging glue.

[0125] Table 1 Performance test

[0126] Brightness / cd UL94 rating LOI / % Stripping Package lamp beads 1# 572 V-0 34.4 No peeling Package lamp beads 2# 566 V-0 34.7 No peeling Package lamp beads 3# 575 V-0 34.7 No peeling Package lamp beads 4# 571 V-0 33.9 No peeling Package lamp beads 5# 568 V-0 33.7 No peeling Package lamp beads 6# 566 V-0 34.2 No peeling Package lamp beads 7# 565 V-0 34.1 No peeling Package lamp beads 8# 570 V-0 34.6 No peeling Package lamp beads 9# 563 V-0 34.1 No peeling Package lamp beads 10# 571 V-0 36.8 No peeling Package lamp beads 11# 573 V-0 34.3 No peeling Package lamp beads 12# 577 No level 26.1 No peeling Package lamp beads 13# 246 V-2 30.5 Stripping

[0127] From the test comparison in Table 1, it can be seen that by comparing the embodiments of the present invention with the comparative examples, it can be seen that, compared with comparative example 1 (without adding flame retardant) and comparative example 2 (adding flame retardant ammonium polyphosphate), the use of the resin composition of the present invention (Examples 1 to 13) can reach UL-94V-0 level, the LOI value can reach 33%-37%, and the encapsulated lamp beads obtained by encapsulation have high brightness and good reliability.

[0128] 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. LED packaging glue, characterized in that: The raw materials of the LED encapsulation adhesive include component A and component B; The component A comprises epoxy resin; The component B includes a curing agent and a curing accelerator; The component A and / or the component B contains a compound shown in formula I: Wherein, R1 and R2 are each independently selected from substituted or unsubstituted aryl, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted C 1-10 Alkoxy, substituted or unsubstituted amine, n≥2, n is an integer.

2. The LED packaging adhesive according to claim 1, characterized in that: The aryl group is a phenyl group; and / or, the C 1-10 Alkyl is methyl, tritiated methyl, ethyl, tert-butyl; and / or, the aryloxy group is a phenoxy group; and / or, the C 1-10 Alkoxy is methoxy, ethoxy, propoxy; And / or, the amine group is amine group, methylamine group, ethylamine group; The substituted or unsubstituted aryl group has a substituent I, and the substituent I is selected from a hydrogen atom, a deuterium atom, a C 1-10 Any of alkyl, cyano, acyl, amino, nitroso, nitro, and hydroxyl; The substituted or unsubstituted C 1-10 The alkyl group has a substituent II, and the substituent II is selected from any one of a hydrogen atom, a deuterium atom, a cyano group, an acyl group, an amino group, a nitroso group, a nitro group, a hydroxyl group, and a phenoxy group; The substituted or unsubstituted aryloxy group has a substituent group III, and the substituent group III is selected from a hydrogen atom, a deuterium atom, a C 1-10 Any of alkyl, cyano, acyl, amino, nitroso, nitro, and hydroxyl; The substituted or unsubstituted C 1-10 The alkoxy group has a substituent IV, and the substituent IV is selected from any one of a hydrogen atom, a deuterium atom, a cyano group, an acyl group, an amino group, a nitroso group, a nitro group, a hydroxyl group, and a phenoxy group; The substituted or unsubstituted C 1-10 The amine group has a substituent V, and the substituent IV is selected from a hydrogen atom, a C 1-10 Any of an alkyl group and a phenyl group.

3. The LED packaging adhesive according to claim 1, characterized in that: The weight ratio of component A to component B is 100:(0.1-200); and / or, in the component B, the ratio of the curing agent to the curing agent accelerator is 100:0.1-20; And / or, in the component B, the ratio of the curing agent to the curing agent accelerator is 100:(1-5).

4. The LED packaging adhesive according to claim 1, characterized in that: The compound represented by formula I is a phosphazene compound; Among the raw materials of the LED packaging glue, the phosphazene compound accounts for 5% to 50% of the total mass of the raw materials; Or, in the raw materials of the LED packaging glue, the phosphazene compound accounts for 10% to 30% of the total mass of the raw materials; The phosphazene compound is selected from one or more of cyclophosphazene and linear polyphosphazene; When the phosphazene compound is cyclophosphazene, n=3 to 8; When the phosphazene compound is a linear polyphosphazene, n≥2.

5. The LED packaging adhesive according to claim 4, characterized in that: The cyclophosphazene is selected from one or more of phenoxy cyclotriphosphazene, tris(o-phenylenedioxy)cyclophosphazene, hexamethoxy cyclotriphosphazene, hexa(deuterated methyl)cyclotriphosphazene, hexa(4-tert-butylphenoxy)cyclotriphosphazene, hexa(4-methylphenoxy)cyclotriphosphazene, hexa(p-aminophenoxy)cyclotriphosphazene, hexa(p-nitrophenoxy)-cyclotriphosphazene, hexa(4-carboxyphenoxy)cyclotriphosphazene, hexaaminocyclotriphosphazene, hexa(3,5-dicarboxyphenoxy)cyclotriphosphazene, and cyclotriphosphazene-PMMH-6 polymer; And / or, the linear polyphosphazene is selected from hexaphenyltriphosphazene, poly(4-nitrophenoxy)phosphazene, phenoxy polyphosphazene, poly(di(methoxy)phosphazene), polybis(methoxyethoxyethoxy)phosphazene, ethoxy polyphosphazene, propoxy polyphosphazene, cyclobutyloxy polyphosphazene, cyclopentyloxy polyphosphazene, ethylamino polyphosphazene, propylamino polyphosphazene, 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2Λ5,4Λ5-bis(phosphorus nitrogen-based compound), poly[bis(alkoxy)(aryloxy)phosphazene], poly[bis(1-(ethoxycarbonyl)-2-phenylethylamino)phosphazene], 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2Λ5,4Λ5-bis(phosphorus nitrogen-based compound) One or more.

6. The LED packaging adhesive according to claim 1, characterized in that: The epoxy resin is selected from at least one of glycidyl ester epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin and alicyclic epoxy resin; The glycidyl ester epoxy resin is selected from at least one of diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl terephthalate, diglycidyl isophthalate, diglycidyl tetrahydrophthalate, diglycidyl methyltetrahydrophthalate, diglycidyl endomethyltetrahydrophthalate, diglycidyl adipate and 2,3-epoxypropyl acrylate; The glycidylamine epoxy resin is selected from at least one of triglycidyl triisocyanate, triglycidyl p-aminophenol, tetraglycidyl diaminodiphenylmethane, tetramethylisopropylphenylene tetraglycidylamine, N,N,N',N'-tetraepoxypropyl-4,4-diaminodiphenylmethane, N,N,N",N-tetraglycidyl-4,4'-methylenedi-o-toluidine, 4,4-diaminodiphenyl ether tetraglycidylamine and diaminodiphenylmethane tetraglycidylamine; The glycidyl ether epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, dicyclopentadiene diepoxy, 3,4-epoxycyclohexylmethyl-2',3'-epoxycyclohexyl ether, ethylene glycol glycidyl ether, 1,4-butanediol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether and 2,2'-((propane-2,2-diylbis(4,1-phenylene))bis(methylene))bis(ethylene oxide); The alicyclic epoxy resin is selected from bis(3,4-epoxycyclohexylmethyl)adipate, 3',4'-epoxycyclohexanemethyl 3,4-epoxycyclohexanecarboxylate, 3',4'-epoxy-6'-methylcyclohexanemethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, 2,2-bis(3,3"-epoxycyclohexyl)propane, bis-(2,3-epoxycyclohexane), 1,2 - at least one of bis-(2,3-epoxycyclohexyloxy)-ethane, bis-(2,3-epoxycyclohexyl) ether, 1,1-bis(2',3'-epoxycyclohexyloxymethyl)-3,4-epoxycyclohexane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, cis-bis-(2,3-epoxycyclopentyl)-ether and trans-bis-(2,3-epoxycyclopentyl)-ether.

7. The LED packaging adhesive according to claim 1, characterized in that: The curing agent is selected from at least one of an amine curing agent, an acid anhydride curing agent, a polyamide resin, a phenolic resin, an imidazole curing agent, a boron trifluoride-amine complex and a cationic curing agent; the relative molecular mass of the polyamide resin is less than 10000; The amine curing agent is selected from at least one of diethylenetriamine, tetramethylenepentamine, hexamethylenediamine, diethylaminopropylamine, meta-xylene diamine, meta-phenylenediamine, dicyandiamide, 1-piperazineethylamine, bismaleimide and phthalazinone; The acid anhydride curing agent is selected from at least one of phthalic anhydride, methylhexahydrophthalic anhydride, dodecylsuccinic anhydride and polyazelaic anhydride; The polyamide resin is selected from at least one of polylaurolactam, polyhexamethylene adipamide, polyamide 651 and polyamide 650; The phenolic resin is selected from at least one of bisphenol A-based phenolic resin and linear phenolic resin; The imidazole curing agent is selected from at least one of 2-methylimidazole and 2-ethyl-4,2-methylimidazole; The boron trifluoride-amine complex is selected from at least one of boron trifluoride monoethylamine and boron trifluoride aniline; The cationic curing agent is at least one selected from triarylsulfonium salts, triarylsulfonium hexafluorophosphates, diaryliodonium salts and bis(4-tert-butylphenyl)iodonium tetraphenylborate.

8. The LED packaging adhesive according to claim 1, characterized in that: The curing accelerator is selected from one or more of substituted urea, metal salt of acetylacetone, metal salt of carboxylic acid and its complex, quaternary ammonium salt, organic guanidine, organic phosphine and peroxide; The substituted urea is selected from N-(4-chlorophenyl) dimethyl urea; The acetylacetonate metal salt is selected from at least one of zinc acetylacetonate, copper acetylacetonate, neodymium acetylacetonate and aluminum acetylacetonate; The thiourea and its derivatives are selected from at least one of thiourea, ethylenethiourea and allylthiourea; The peroxide is selected from at least one of di-tert-butyl peroxide, tert-butyl peroxybenzoate and benzoyl peroxide; The organic guanidine is selected from tetramethylguanidine; The organic phosphine is selected from at least one of triphenylphosphine, tetraphenylphosphine bromide and tetrabutylphosphonium acetate; The carboxylic acid metal salt and its complex are selected from at least one of zinc naphthenate, cobalt naphthenate, manganese naphthenate and zinc isooctanoate; The quaternary ammonium salt is selected from at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide and tetraethylammonium hydroxide.

9. The LED packaging adhesive according to claim 1, characterized in that: The flame retardant performance of the LED packaging adhesive under the condition of 25° C. is UL-94V-0 grade, and the LOI value is 32% to 37%.

10. The method for preparing the LED encapsulation adhesive according to any one of claims 1 to 9, characterized in that: In component A, epoxy resin and phosphazene compound are mixed at 60-100°C; In component B, the curing agent, curing accelerator and phosphazene are mixed at 60-100°C; The component A is mixed with the component B to obtain the LED packaging adhesive.

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