Preparation method of organic phosphorus compound, epoxy molding compound and application thereof

Abstract

This invention relates to the field of epoxy molding compound technology, specifically to a method for preparing an organophosphorus compound, an epoxy molding compound, and its applications. The method includes: reacting tetraphenylphosphine bromide with 2,3-dihydroxynaphthalene in the presence of an alkaline solution and an organic solvent to obtain an organophosphorus compound. The obtained organophosphorus compound is added as a curing accelerator to a raw material composition, and the epoxy molding compound is prepared by adding a mercapto-free coupling agent and controlling the proportions between the raw material components. The epoxy molding compound prepared by this invention is odorless and environmentally friendly, and has high copper adhesion, resulting in higher reliability in semiconductor applications.

Description

Technical Field

[0001] This invention relates to the field of epoxy molding compound technology, specifically to a method for preparing an organophosphorus compound, an epoxy molding compound, and its applications. Background Technology

[0002] Epoxy molding compounds are widely used in the semiconductor packaging industry due to their advantages such as low shrinkage, excellent electrical insulation properties, chemical resistance, easy processing, low cost, and convenient mass production, occupying 97% of the entire microelectronic packaging materials market.

[0003] With the development of the times, people have increasingly higher requirements for production and packaging environments, and their environmental awareness is also growing stronger. Some of the raw material compositions used in the preparation of epoxy molding compounds are chemically synthesized from different organic compounds. These compositions themselves carry the odor of byproducts and solvents produced during the reaction process. These raw material compositions are mixed together through mechanical blending and then melt-extruded to prepare epoxy molding compounds. The melting temperature is generally quite high, which causes some volatile substances in the raw material compositions to volatilize to the maximum extent, thus placing a series of health burdens on the relevant workers. Summary of the Invention

[0004] The purpose of this invention is to address the shortcomings of existing technologies by providing a method for preparing organophosphorus compounds, an epoxy molding compound, and their applications. This invention first reacts tetraphenylphosphine bromide with 2,3-dihydroxynaphthalene under certain conditions to generate an organophosphorus compound. Then, the obtained organophosphorus compound is added to the raw material composition as a curing accelerator. By adding a mercapto-free coupling agent and controlling the proportions between the raw material components, the prepared epoxy molding compound is odorless, environmentally friendly, and possesses high copper adhesion, resulting in higher reliability in semiconductor applications.

[0005] To achieve the above objectives, the first aspect of the present invention provides a method for preparing organophosphorus compounds, the method comprising: a complexation reaction of tetraphenylphosphine bromide with 2,3-dihydroxynaphthalene in the presence of an alkaline solution and an organic solvent.

[0006] Preferably, the molar ratio of the tetraphenylphosphine bromide to the 2,3-dihydroxynaphthalene is 1-5:2-8.

[0007] Preferably, the conditions for the complexation reaction include: a reaction temperature of 5-20°C and a reaction time of 1-4 hours.

[0008] A second aspect of the present invention provides an epoxy molding compound, wherein the epoxy molding compound is prepared from a raw material composition containing 3-15% by weight of epoxy resin, 2-10% by weight of phenolic resin, 0.05-2.0% by weight of curing accelerator, 70-90% by weight of filler, 0.1-1.2% by weight of release agent, 0.2-1.4% by weight of toughening agent, 0.3-2% by weight of coupling agent, and 0-2% by weight of colorant.

[0009] The coupling agent is a mercapto-free coupling agent, and the curing accelerator contains the organophosphorus compound A mentioned above, as well as one or more of the optional tertiary amine compound, organophosphorus compound B, and imidazole compound.

[0010] Preferably, the content of organophosphorus compound A is 5-100% by weight, based on 100% by weight of the total weight of the curing accelerator.

[0011] Preferably, the tertiary amine compound is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undec-7-ene, and triethylamine benzyldimethylamine.

[0012] Preferably, the organophosphorus compound B is selected from one or more of triphenylphosphine, triethylphosphine, trimethylphosphine, tributylphosphine, and tris(p-tolyl)phosphine.

[0013] Preferably, the imidazole compound is selected from one or more of 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-heptadecylimidazole and 3-amino-1,2,4-triazole.

[0014] Preferably, the mercapto-free coupling agent is selected from one or more of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl ethertrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysiloxane.

[0015] Preferably, the toughening agent is selected from one or more of the following: methyl methacrylate-butadiene-styrene terpolymer, acrylonitrile-butadiene-styrene copolymer, chlorinated polyethylene, and ethylene-vinyl acetate copolymer.

[0016] Preferably, the median diameter of the packing is 5-80 μm.

[0017] A third aspect of the present invention provides an application of the epoxy molding compound described above as a semiconductor packaging material.

[0018] Through the above technical solution, the present invention first reacts tetraphenylphosphine bromide with 2,3-dihydroxynaphthalene under certain conditions to generate an organophosphorus compound, and then adds the obtained organophosphorus compound as a curing accelerator to the raw material composition. By adding a mercapto-free coupling agent and controlling the ratio between the raw material components, the prepared epoxy molding compound is odorless and environmentally friendly, and has high copper adhesion, resulting in higher reliability in semiconductor applications. Detailed Implementation

[0019] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0020] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0021] The inventors discovered through research that reacting tetraphenylphosphine bromide with 2,3-dihydroxynaphthalene under certain conditions generates an organophosphorus compound. The resulting organophosphorus compound is then added to the raw material composition as a curing accelerator. By adding a mercapto-free coupling agent and controlling the proportions between the raw material components, the prepared epoxy molding compound is odorless and environmentally friendly, and has high copper adhesion, resulting in higher reliability in semiconductor applications.

[0022] The first aspect of the present invention provides a method for preparing organophosphorus compounds, the method comprising: a complexation reaction of tetraphenylphosphine bromide with 2,3-dihydroxynaphthalene in the presence of an alkaline solution and an organic solvent.

[0023] In the method described in this invention, in a specific embodiment, the alkaline solution may be one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, and sodium carbonate.

[0024] In the method described in this invention, in specific embodiments, the organic solvent may be one or more of methanol, toluene, dichloromethane, and methyltetrahydrofuran.

[0025] In the method described in this invention, in a specific embodiment, the molar ratio of the amount of tetraphenylphosphine bromide to the amount of 2,3-dihydroxynaphthalene is 1-5:2-8, for example, it can be 1:2, 3:4, 3:5, 4:7 or 5:8.

[0026] In the method described in this invention, in a specific embodiment, the conditions for the complexation reaction include: a reaction temperature of 5-20°C, for example, 5°C, 8°C, 10°C, 13°C, 16°C, or 20°C; and a reaction time of 1-4 hours, for example, 1 hour, 1.5 hours, 2 hours, 3 hours, or 4 hours.

[0027] In the method described in this invention, in a specific embodiment, the reaction formula for preparing organophosphorus compounds includes:

[0028]

[0029] A second aspect of the present invention provides an epoxy molding compound, wherein the epoxy molding compound is prepared by means of a raw material composition containing 3-15% by weight of epoxy resin, 2-10% by weight of phenolic resin (curing agent), 0.05-2.0% by weight of curing accelerator, 70-90% by weight of filler, 0.1-1.2% by weight of release agent, 0.2-1.4% by weight of toughening agent, 0.3-2% by weight of coupling agent and 0-2% by weight of colorant.

[0030] The coupling agent is a mercapto-free coupling agent, and the curing accelerator contains the organophosphorus compound A mentioned above, as well as one or more of the optional tertiary amine compound, organophosphorus compound B, and imidazole compound.

[0031] In the epoxy molding compound of the present invention, in a specific embodiment, the organophosphorus compound A is the compound shown in formula (1).

[0032]

[0033] in, As a ligand, It is the central ion.

[0034] In the epoxy molding compound of the present invention, in a specific embodiment, based on the total weight of the curing accelerator as 100% by weight, the content of the organophosphorus compound A is 5-100% by weight, for example, it can be 5% by weight, 10.5% by weight, 17% by weight, 24% by weight, 31% by weight, 40% by weight, 50% by weight, 64% by weight, 80% by weight, 90% by weight, or 100% by weight.

[0035] In the epoxy molding compound of the present invention, in a preferred embodiment, the tertiary amine compound is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undec-7-ene, and triethylamine benzyldimethylamine.

[0036] In the epoxy molding compound of the present invention, in a preferred embodiment, the organophosphorus compound B is selected from one or more of triphenylphosphine, triethylphosphine, trimethylphosphine, tributylphosphine, and tris(p-tolyl)phosphine.

[0037] In the epoxy molding compound of the present invention, in a preferred embodiment, the imidazole compound is selected from one or more of 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-heptadecylimidazole and 3-amino-1,2,4-triazole.

[0038] In the epoxy molding compound of the present invention, in a specific embodiment, the mercapto-free coupling agent is selected from one or more of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl ether trimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysiloxane.

[0039] In the epoxy molding compound of the present invention, in a specific embodiment, the toughening agent is selected from one or more of the following: methyl methacrylate-butadiene-styrene terpolymer, acrylonitrile-butadiene-styrene copolymer, chlorinated polyethylene, and ethylene-vinyl acetate copolymer.

[0040] In the epoxy molding compound of this invention, the epoxy resin is a conventional choice in the art. In a preferred embodiment, the epoxy resin is selected from one or more of o-cresol epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, aliphatic glycidyl ether epoxy resin, and heterocyclic epoxy resin.

[0041] In the epoxy molding compound of this invention, the phenolic resin is a conventional choice in the art. In a preferred embodiment, the phenolic resin is selected from one or more of the following: linear phenolic resin and its derivatives, condensates of p-xylene and phenol, condensates of p-xylene and naphthol, copolymers of dicyclopentadiene and phenol, linear phenolic resin and its derivatives, and monohydroxy or dihydroxynaphthol phenolic resin and its derivatives.

[0042] In the epoxy molding compound of this invention, the filler is a conventional choice in the art. In a preferred embodiment, the filler is selected from one or more of alumina, titanium dioxide, silicon nitride, and silicon dioxide. In a more preferred embodiment, the median diameter of the filler is 5-80 μm. In a further preferred embodiment, the silicon dioxide is crystalline silicon dioxide and / or molten silicon dioxide.

[0043] In the epoxy molding compound of this invention, the release agent is a conventional choice in the art. In a preferred embodiment, the release agent is selected from one or more of polyethylene wax, carnauba wax, synthetic wax, and mineral wax.

[0044] In the epoxy molding compound of this invention, the colorant is a conventional choice in the art. In a preferred embodiment, the colorant is selected from one or more of titanium dioxide, zinc oxide, and carbon black.

[0045] The preparation method of the epoxy molding compound described in this invention is a conventional choice in the art. The specific preparation method may include: weighing each component according to a specific ratio, pulverizing and mixing them evenly at room temperature, then melting and kneading, pulverizing, and mixing to obtain an epoxy resin composition.

[0046] In this invention, the equipment used for melt mixing can be a conventional choice in the art, such as a two-roll open mill, a single-screw extruder, a twin-screw extruder, a kneader, or a mixer.

[0047] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited thereto.

[0048] Unless otherwise specified, all reagents used in the embodiments and comparative examples of this invention are commercially available products.

[0049] A1 epoxy resin: Biphenyl phenol epoxy resin, manufacturer: Nippon Kayaku Co. Ltd., grade: NC3000;

[0050] B1 Phenolic Resin: Biphenyl-type aryl phenolic resin, manufacturer: (Meiwa Plastic Industries, Ltd., grade: MEH-7851ss);

[0051] C1 curing accelerator: an organophosphorus compound with the chemical formula shown in formula (1).

[0052]

[0053] C2 curing accelerator: 3-amino-1,2,4-triazole, manufacturer: Aladdin, brand: ATA;

[0054] D filler: silica, manufacturer: Jiangsu Lianrui, d50 is 22μm;

[0055] E-release agent: Carnauba wax, manufacturer: Shanghai Yiba Chemical Raw Materials Co., Ltd., grade: t3;

[0056] Toughening agent F: Methyl methacrylate-butadiene-styrene terpolymer, manufacturer: Shenzhen Yingshun Plastic Raw Materials Co., Ltd., brand: MBS;

[0057] G1 Coupling Agent: γ-glycidoxypropyltrimethoxysilane, Manufacturer: Dow Corning, Grade: Z-6040;

[0058] G2 coupling agent: N-phenyl-3-aminopropyltrimethoxysiloxane, manufacturer: Dow Corning, grade: Y-9669;

[0059] G3 Coupling Agent: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, Manufacturer: Nanjing Nengde Chemical Co., Ltd., Grade: KH566;

[0060] H. Colorant: Carbon black, Manufacturer: Hengdeli Chemical Co., Ltd.

[0061] Example C1 and Comparative Examples C1-1 to C1-2 are used to illustrate the preparation process of organophosphorus compounds.

[0062] Example C1

[0063] The preparation process of organophosphorus compounds includes: in the presence of sodium hydroxide and methanol, 1 mol of tetraphenylphosphine bromide and 2 mol of 2,3-dihydroxynaphthalene are complexed to generate organophosphorus compound C1.

[0064] Comparative Example C1-1

[0065] In the presence of sodium hydroxide, 1 mol of tetraphenylphosphine bromide and 2 mol of 2,3-dihydroxynaphthalene are complexed to generate organophosphorus compound C1-1.

[0066] Comparative Example C1-2

[0067] Tetraphenylphosphine bromide was directly used as C1-2.

[0068] Examples 1-11 and Comparative Examples 1-11 are used to illustrate the preparation process of epoxy molding compounds.

[0069] The raw material components of Examples 1-11 and Comparative Examples 1-11 were proportioned according to Tables 1 and 2, respectively, and were carried out according to the following methods:

[0070] (1) Weigh each raw material component, then mix the raw material composition, and melt-mix the mixed material on an open mixing mill with a main roller at 80°C and an auxiliary roller at 100°C for 10 minutes.

[0071] (2) Cool and crush the molten compound obtained in step (1) and preform it into cake to obtain epoxy molding compound.

[0072] Table 1 Raw material ratios for Examples 1-11

[0073]

[0074]

[0075] Table 2 Raw material ratios for Comparative Examples 1-8

[0076]

[0077] Comparative Example 9

[0078] The preparation method and raw material ratio of Example 1 were followed, except that the coupling agent was replaced with 0.75g of 3-mercaptopropyltrimethoxysilane.

[0079] Comparative Example 10

[0080] The preparation method and raw material ratio of Example 1 were followed, except that all C1 was replaced with C1-1.

[0081] Comparative Example 11

[0082] The preparation method and raw material ratio of Example 1 were followed, except that all C1 was replaced with C1-2.

[0083] Test case

[0084] Copper adhesion before post-curing, copper adhesion after post-curing:

[0085] Using a low-pressure transfer molding machine at a mold temperature of 175℃, an injection pressure of 60 bar, and a curing time of 110 seconds, the resulting epoxy molding compound was molded onto a copper sheet to form a contact area of ​​176 mm². 2 A cylindrical object was used, with half of the pre-cured epoxy molding compound undergoing post-curing. The copper adhesion strength (N) of the uncured and post-cured components was tested using a computer-controlled electronic universal testing machine.

[0086] The copper adhesion before and after post-curing of the epoxy molding compounds prepared in Examples 1-11 and Comparative Examples 1-11 were tested, and the results are shown in Table 3.

[0087] Table 3

[0088]

[0089]

[0090] The test results of Examples 1-11 and Comparative Examples 1-11 show that the epoxy molding compound prepared using the mercapto-free coupling agent has no pungent odor. At the same time, the organic phosphorus compound generated by the reaction of tetraphenylphosphine bromide with 2,3-dihydroxynaphthalene under certain conditions is added to the raw material composition as a curing accelerator, and the proportion between each raw material component is controlled, so that the prepared epoxy molding compound has high copper adhesion and higher reliability in semiconductor applications.

[0091] The above are merely embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent modifications made based on the content of the present invention specification, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. An epoxy molding compound, characterized in that, Based on the total weight of the raw material composition used to prepare the epoxy molding compound (100% by weight), the epoxy molding compound is made from a raw material composition containing 3-15% by weight of epoxy resin, 2-10% by weight of phenolic resin, 1.2-2.0% by weight of curing accelerator, 70-90% by weight of filler, 0.1-1.2% by weight of release agent, 0.2-1.4% by weight of toughening agent, 1.5-2% by weight of coupling agent, and 0-2% by weight of colorant. The coupling agent is a mercapto-free coupling agent, and the curing accelerator is an organophosphorus compound A and 3-amino-1,2,4-triazole. Based on the total weight of the curing accelerator as 100% by weight, the weight content of organophosphorus compound A is: ~ ; The mercapto-free coupling agent is γ-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane. The method for preparing the organophosphorus compound A includes: a complexation reaction between tetraphenylphosphine bromide and 2,3-dihydroxynaphthalene in the presence of an alkaline solution and an organic solvent.

2. The epoxy molding compound according to claim 1, characterized in that, The molar ratio of the tetraphenylphosphine bromide to the 2,3-dihydroxynaphthalene is 1-5:2-8.

3. The epoxy molding compound according to claim 1, characterized in that, The conditions for the complexation reaction include: a reaction temperature of 5-20℃ and a reaction time of 1-4h.

4. The epoxy molding compound according to claim 1, characterized in that, The toughening agent is selected from one or more of the following: methyl methacrylate-butadiene-styrene terpolymer, acrylonitrile-butadiene-styrene copolymer, chlorinated polyethylene, and ethylene-vinyl acetate copolymer.

5. The epoxy molding compound according to claim 1, characterized in that, The median diameter of the packing is 5-80 μm.

6. The application of the epoxy molding compound according to any one of claims 1-5 as a semiconductor packaging material.

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