TW201520262A - Halogen-free epoxy resin composition applicable to IC packaging - Google Patents

Abstract

The present invention discloses a halogen-free epoxy resin composition applicable to IC packaging. The resin composition comprises polyfunctional epoxy resin, benzoxazine resin, phosphorus-containing curing agent, inorganic filler, curing accelerator and solvent. The composition contains resin with both of better rigidity and toughness, and low expansion coefficient and excellent heat resistance given by the inorganic filler, so that the laminated plate prepared from the composition is applicable to IC packaging substrate, and the laminated plate prepared from the above-described composition is halogen-free, having flame-retarding grade of UL94-V0.

Description

Halogen-free epoxy resin composition for IC packaging

The present invention relates to a halogen-free epoxy resin composition for IC packaging.

With the further development of the digital age, the thinness and high speed of electronic products have become a trend, and for PCBs, this means that the thin thin wire small hole size is accurate and stable, and the cost is low. Under the guidance of this trend, PCB IC packaging technology has also made great progress, from the PTH Insertion before the 1980s, to the surface-mounted SMT method from 1980 to 1993, and then progressed to Up to now, BGA, CSP, FC and LGA are the main construction methods. However, with the development of packaging technology, the requirements for IC package substrates are getting higher and higher.

In order to meet the requirements of miniaturization, high density, and high frequency, the materials used in the IC substrate must have good heat resistance and a low expansion coefficient. Ordinary FR-4 epoxy system substrates are difficult to meet this demand due to the high expansion coefficient, while special resin systems such as Bima-triazine resin (BT), polyphenylene ether (PPE) resin, and polytetrafluoroethylene. Although the (PTFE) resin has an excellent expansion coefficient, it is much higher than the price of a common substrate and a special processing technology, which limits the further development of the IC package. Therefore, the development of a low-cost IC package substrate becomes an urgent Market demand.

In view of the above, the present invention is directed to the absence of the prior art, and its main object is to provide a halogen-free epoxy resin composition for IC packaging, which has a low expansion coefficient, good heat resistance, and dielectric properties. Low loss, high glass transition temperature and good flame retardancy.

In order to achieve the above object, the present invention adopts the following technical solution: a halogen-free epoxy resin composition for IC packaging, comprising:

(a) a polyfunctional epoxy resin; (b) a benzoxazine resin; (c) a phosphorus-containing curing agent; (d) an inorganic filler; (e) a curing accelerator; (f) a decane coupling agent; The polyfunctional epoxy resin (a) is 15 to 45 parts by mass based on 100 parts by mass based on the total weight of the components (a), (b) and (c); and the benzoxazine resin (b) is 8 to 8 parts by weight. 29 parts by mass; the phosphorus-containing curing agent (c) is 30 to 60 parts by mass; the inorganic filler (d) is 60% to 220% of the total weight of the components (a), (b) and (c); the curing accelerator (e) is 0.01% to 1% by weight based on the total weight of the components (a), (b) and (c); the decane coupling agent (f) is 0.01 of the total weight of the components (a), (b) and (c) %~1%.

The benzoxazine is a phenolphthalein type benzoxazine, and its structural formula is: .

The polyfunctional epoxy resin is one or more of a trifunctional epoxy resin, a DCPD modified epoxy resin, a tetramethylbiphenyl epoxy resin, a biphenyl epoxy resin, and a naphthalene ring epoxy resin. The structural formula is: trifunctional epoxy resin ; DCPD modified epoxy resin ; tetramethylbiphenyl epoxy resin ; biphenyl epoxy resin ; naphthalene ring epoxy resin .

The phosphorus-containing curing agent is a modified phenol resin having a DOPO or DOPO derivative structure.

The inorganic filler is one or more of cerium oxide, spherical cerium oxide, cerium aluminate, kaolin, and talc.

The curing accelerator is an imidazole curing accelerator comprising one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole .

The invention has obvious advantages and beneficial effects compared with the prior art, and the beneficial effects of the invention are as follows:

1. A benzoxazine resin having a phenolphthalein structure contained in the composition, which has strong rigidity and heat resistance, and has a higher glass transition temperature than a common benzo resin.

2. The polyfunctional epoxy resin contained in the composition has a rigid group such as a naphthalene ring or a biphenyl group contained in the structure, and has a positive effect on lowering the expansion coefficient of the resin, and also has good electrical properties. Heat resistance and high glass transition temperature.

3. The phosphorus-containing curing agent contained in the composition provides a good flame retardant effect, so that the flame retardancy of the compound reaches the V0 standard.

4. The inorganic filler contained in the composition can greatly reduce the expansion coefficient of the composition, and at the same time reduce the cost and improve the flame retardancy.

5. A copper-clad laminate suitable for packaging a carrier plate made of the composition has low thermal expansion coefficient, high heat resistance, high glass transition temperature (Tg), flame retardancy, low dielectric loss and the like.

A halogen-free epoxy resin composition for IC packaging, comprising:

(A) Epoxy resin.

A 1: Naphthalene ring epoxy resin.

A 2: tetramethylbiphenyl epoxy resin.

A 3: a trifunctional epoxy resin.

A 4: BPA type epoxy resin.

(B) A thermosetting resin containing a compound having dihydrobenzoxazine as a main component.

B1: phenolphthalein type benzoxazine resin.

B2: BPA type benzoxazine resin.

(C) phenolic resin.

C1: Phosphorus-containing phenolic resin.

C2: Novolac resin.

(D) Accelerator.

D: diethyltetramethylimidazole.

(E) Coupling agent.

E: decane coupling agent.

(F) Inorganic filler.

F1: molten cerium oxide.

F2: spherical cerium oxide.

The above resin was dissolved and mixed according to the ratio of Table 1, and then immersed and coated on the glass fiber cloth of reinforcing material, baked in an oven at 171 ° C for 3 to 5 minutes to obtain a prepreg, and 8 sheets of prepreg were coated with 10Z copper foil. The laminate was laminated in a laminator to obtain a laminate, and the laminate was subjected to characteristic evaluation.

Table 1 Formulation of the composition (1) (parts by mass)

Table 2 Characteristics Evaluation 1

Table 3 Characteristic Evaluation 2

The test methods for the above characteristics are as follows:

(1) Water absorption: The ratio of the difference in weight before and after PCT cooking for 1 h relative to the weight of the sample before PCT.

(2) The PCT was cooked in a 115 ° C 105 KPa pressure cooker for 1 h, immersed in a 288 ° C tin furnace, and the burst delamination time was recorded.

(3) Float (Cu): The copper-containing sample was floated on the surface of the tin bath at 288 ° C, and the delamination time of the burst was recorded.

(4) Thermal stratification time T-288: Measured according to the method of IPC-TM-650 2.4.24.1.

(5) Thermal expansion coefficient Z-axis CTE (TMA): Measured according to IPC-TM-650 2.4.24.

(6) Glass transition temperature (Tg): Measured according to the differential scanning calorimetry (DSC) according to the DSC method specified in IPC-TM-6502.4.25.

(7) Dielectric loss tangent: The dielectric loss tangent at 1 GHz was measured using the parallel plate method according to IPC-TM-6502.5.5.9.

(8) Flammability: Measured according to UL 94 vertical burning method.

In summary, the halogen-free low-expansion resin composition for an IC package substrate of the present invention contains no halogen, and has a flame retardancy of UL94V-0; a copper-clad for use in a package carrier using the composition The foil laminate has a very low coefficient of thermal expansion, high heat resistance, high glass transition temperature (Tg), flame retardancy, low dielectric loss and the like.

The above is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention. Therefore, any minor modifications, equivalent changes and modifications made to the above embodiments in accordance with the technical spirit of the present invention are Still falling within the scope of the technical solution of the present invention.

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Claims (6)

A halogen-free epoxy resin composition for IC encapsulation, comprising: (a) a polyfunctional epoxy resin; (b) a benzoxazine resin; (c) a phosphorus-containing curing agent; (d) an inorganic (e) a curing accelerator; (f) a decane coupling agent; wherein the polyfunctional epoxy resin (a) is 100 parts by mass based on the total weight of the components (a), (b) and (c) ) is 15 to 45 parts by mass; the benzoxazine resin (b) is 8 to 29 parts by mass; the phosphorus-containing curing agent (c) is 30 to 60 parts by mass; and the inorganic filler (d) is the component (a), b) and (c) 60% to 220% of the total weight; the curing accelerator (e) is 0.01% to 1% of the total weight of the components (a), (b) and (c); the decane coupling agent ( f) is 0.01% to 1% of the total weight of the components (a), (b) and (c). The halogen-free epoxy resin composition for IC encapsulation according to claim 1, wherein the benzoxazine resin is a phenolphthalein type benzoxazine resin, and the structural formula is: . The halogen-free epoxy resin composition for IC package according to claim 1, wherein the polyfunctional epoxy resin is a trifunctional epoxy resin, a DCPD modified epoxy resin, or a tetramethylbiphenyl ring. One or more of an oxygen resin, a biphenyl epoxy resin, and a naphthalene ring epoxy resin, and the structural formula is: a trifunctional epoxy resin ; DCPD modified epoxy resin ; tetramethylbiphenyl epoxy resin ; biphenyl epoxy resin ; naphthalene ring epoxy resin . The halogen-free epoxy resin composition for IC encapsulation according to claim 1, wherein the phosphorus-containing curing agent is a modified phenol resin having a DOPO or DOPO derivative structure. The halogen-free epoxy resin composition for IC package according to claim 1, wherein the inorganic filler is one or more of cerium oxide, spherical cerium oxide, strontium aluminate, kaolin, and talc. . The halogen-free epoxy resin composition for IC encapsulation according to claim 1, wherein the curing accelerator is an imidazole curing accelerator comprising 2-methylimidazole and 2-ethyl-4-methyl One or more of imidazole, 2-phenylimidazole, 2-undecylimidazole.