Thermosetting resin composition for semiconductor package and prepreg and metal clad laminate using the same

Abstract

There are provided a thermosetting resin composition for a semiconductor package and a prepreg and a metal clad laminate using the same. More particularly, there are provided a thermosetting resin composition for a semiconductor package capable of improving desmear characteristics by using a cyanate based ester resin and a benzoxazine resin in a thermosetting resin composition based on an epoxy resin and improving chemical resistance by using a slurry type filler to have high heat resistance and reliability, and a prepreg and a metal clad laminate using the same.

Claims

1. A thermosetting resin composition for a semiconductor package comprising: a binder, a slurry filler and a curing accelerator, wherein the binder contains 20 to 30 wt % of a naphthalene epoxy resin, 25 to 73 wt % of a bismaleimide resin, and 5 to 7 wt % of a benzoxazine resin based on a total weight of the binder, wherein the thermosetting resin composition has a viscosity of 20 to 50 cps at a temperature of 20 to 35° C., wherein the thermosetting resin composition does not include a phenolic curing agent, wherein the bismaleimide resin includes 4,4′-bismaleimido-diphenylmethane or a mixture of a bismaleimide-triazine resin and 4,4′-bismaleimido-diphenylmethane, and wherein the curing accelerator is contained in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the binder, wherein the slurry filler comprises an epoxy silane-modified silica dispersed in a solvent, wherein the benzoxazine resin is 3,3-bis(3-phenyl-2,4-dihydro-1,3-benzoxazin-6-yl)-2-benzofuran-1-one, wherein the slurry filler is contained at a content of 180 to 350 parts by weight based on 100 parts by weight of the binder, and wherein the epoxy silane-modified silica is contained at a content of 126 to 245 parts by weight based on 100 parts by weight of the binder.

2. The thermosetting resin composition of claim 1, wherein the binder further contains a phenol novolac cyanate based ester resin, and wherein the cyanate based ester resin has a weight average molecular weight of 200 to 400.

3. The thermosetting resin composition of claim 2, wherein the binder contains 30 to 40 wt % of the cyanate based ester resin.

4. The thermosetting resin composition of claim 1, further comprising at least one additive selected from the group consisting of an additional solvent, a dispersant, and a silane coupling agent.

5. The thermosetting resin composition of claim 1, further comprising a modified bismaleimide resin including a Diels-Alder comonomer selected from the group consisting of styrene and styrene derivatives, bis(propenylphenoxy) compounds, 4,4′bis(propenylphenoxy)sulfone, 4,4′-bis(propenylphenoxy)benzophenone, and 4,4′-1-(1-methylethyllidene)bis(2-(2-propenyl)phenol).

6. A prepreg prepared by impregnating the thermosetting resin composition of claim 1 into a fabric substrate.

7. A metal clad laminate comprising: the prepreg of claim 6; and metal foil integrated with the prepreg by heating and pressurizing.

8. A method of preparing a multilayer printed circuit board for a semiconductor package, comprising: applying a resin varnish to a substrate to form a prepreg; integrating a metal foil with the prepreg by heating and pressurizing to form a metal clad laminate; and processing a circuit on the metal clad laminate to form the multilayer printed circuit board, wherein the resin varnish is the thermosetting resin composition of claim 1.

Description

Examples 1 to 2 and Comparative Examples 1 to 3

(1) Thermosetting resin compositions in Examples and Comparative Examples were prepared by mixing ingredients with each other so as to have compositions and contents as shown in the following Table 1, respectively.

(2) Resin varnish was prepared by mixing the thermosetting resin compositions with a filler, respectively, and then mixing the mixture in a high speed mixer.

(3) Then, the resin varnish was impregnated into glass fabric (1078, manufactured by Nittobo, T-glass) having a thickness of 45 μm and then hot-air-dried at a temperature of 140° C., thereby preparing a prepreg.

(4) In this case, each of the ingredients used to prepare the resin varnish was as follows:

(5) Bismaleimide based resin (BMI-2300, manufactured by DAIWA); BT resin (Nanozine 600, manufactured by Nanokor); novolac type cyanate resin (PT-30S, manufactured by Lonza); naphthalene based epoxy resin (HP4710, manufactured by DIC Corp.); phenolphthalein based benzoxazine resin (XU8282, manufactured by Hunstman); epoxy silane treated slurry type silica (SC2050FNC, manufactured by Admatechs); powder type filler (SFP-30NHE, manufactured by Denka); provided that, a content of the resin ingredients in the following Tables 1 and 2 is based on wt % (sum: 100 wt %), and a content of silica is based on 100 parts by weight of the resin.

(6) Thereafter, after two sheets of the prepreg prepared as described above were laminated, copper foil (thickness: 12 μm, manufactured by Mitsui) was positioned and laminated on both surfaces thereof and heated and pressurized at a temperature of 220° C. and a pressure of 50 kg/cm.sup.2 for 75 minutes using a press, thereby manufacturing a copper clad laminate (thickness: 100 μm).

(7) After etching the copper clad laminate manufactured as described above, basic physical properties and chemical resistance were tested.

(8) TABLE-US-00001 TABLE 1 Example 1 Example 2 Epoxy resin 30 20 Cyanate 40 0 based ester resin BT resin — 45 BMT resin 25 28 Benzoxazine 5 7 resin Curing 0.3 0.3 accelerator Phenolic — — curing agent Inorganic 180 180 filler A Inorganic — — filler B Note) 1) Epoxy resin: naphthalene based epoxy resin(HP4710, DIC) 2) BT resin: BT resin(Nanozine 600, Nanokor) 3) Cyanate based ester resin: novolac type cyanate resin(PT-30S, Lonza) 4) BMT resin: bismaleimide based resin(BMI-2300, DAIWA) 5) benzoxazine resin: phenolphthalene based benzoxazine resin(XU8282, Hunstman) 6) Curing accelerator: phenyl imidazole (2PZ, Shikoku) 7) Phenolic curing agent: cresol-novolac curing agent (GPX-41, Gifu Shellac) 8) Inorganic filler A: epoxy silane treated slurry type silica (SC2050FNC, Admatechs) 9) Inorganic filler B: powder type filler (SFP-30MHE, Denka)

(9) TABLE-US-00002 TABLE 2 Compar- Compar- Compar- Compar- Compar- ative ative ative ative ative Example 1 Example 2 Example 3 Example 4 Example 5 Epoxy resin 20 30 50 30 12 Cyanate 35 40 — 40 16 based ester resin BT resin — — — 0 — BMT resin 30 25 45 25 28 Benzoxazine 15  0 5 5 44 resin Curing — — 0.3 —   0.1 accelerator Phenolic —  5 — — — curing agent Inorganic 180  180  180 — 80 filler A Inorganic — — — 180 — filler B Note) 1) Epoxy resin: naphthalene based epoxy resin (HP4710, DIC) 2) BT resin: BT resin (Nanozine 600, Nanokor) 3) Cyanate based ester resin: novolac type cyanate resin (PT-30S, Lonza) 4) BMT resin: bismaleimide based resin (BMI-2300, DAIWA) 5) benzoxazine resin: phenolphthalene based benzoxazine resin (XU8282, Hunstman) 6) Curing accelerator: phenyl imidazole (2PZ, Shikoku) 7) Phenolic curing agent: cresol-novolac curing agent (GPX-41, Gifu Shellac) 8) Inorganic filler A: epoxy silane treated slurry type silica (SC2050FNC, Admatechs) 9) Inorganic filler B: powder type filler (SFP-30MHE, Denka)

Experimental Example

Evaluation of Physical Properties

(10) Physical properties of the thermosetting resin compositions obtained in Examples and Comparative Examples were evaluated by the following methods.

(11) 1. Evaluation of Viscosity

(12) In order to evaluate flowability of the resin, viscosities of the thermosetting resin compositions obtained in Examples and Comparative Examples were measured at a temperature of 25 using a Brookfield viscometer.

(13) 2. Evaluation of Physical Properties of Copper Clad Laminate

(14) Physical properties of the copper clad laminates manufactured in Examples and Comparative Examples were evaluated by the following methods, and the results were shown in Tables 3 and 4.

(15) (a) Evaluation of Chemical Resistance

(16) In desmear evaluation, an atmosphere of the entire process conditions was alkaline, and processes were performed in a sequence of a swelling process, a permanganate process, and a neutralizing process. As a solvent, an available solution manufactured by Atotech was used.

(17) Chemical resistance was evaluated by etching to remove the copper foil of the copper clad laminate and then measuring a difference (etching rate) in a weight of the sample before and after a desmear process.

(18) (b) Glass Transition Temperature

(19) After etching to remove the copper foil of the copper clad laminate, a glass transition temperature was measured at a heating rate of 5° C./min by dynamic mechanical analysis (DMA).

(20) After etching to remove the copper foil of the copper clad laminate, a glass transition temperature was measured at a heating rate of 10° C./min by thermo mechanical analysis (TMA).

(21) (c) Elastic Modulus

(22) After etching to remove the copper foil of the copper clad laminate, an elastic modulus was measured at 30° C. and 260° C. at a heating rate of 5° C./min by dynamic mechanical analysis (DMA).

(23) (d) Coefficient of Thermal Expansion (CTE)

(24) After etching to remove the copper foil of the copper clad laminate, a coefficient of thermal expansion (CTE) was measured at a heating rate of 10° C./min by thermo mechanical analysis (TMA).

(25) (e) Water Absorption

(26) After etching to remove the copper foil of the copper clad laminate, water absorption was measured using a thermo-hygrostat under 85° C./85% conditions.

(27) (f) Evaluation of Adhesion (Peel Strength)

(28) Peel strength of a section (width: 1 cm) of the copper clad laminate was evaluated using a texture analyzer.

(29) TABLE-US-00003 TABLE 3 Compar- ative Example 1 Example 2 Example 1 Viscosity 40 40 70 (25° C., cps) Desmear 0.003 0.004 0.01 (g/50 cm.sup.2) Glass transition 300 300 290 temperature (DMA) (° C.) Glass transition 270 270 250 temperature (TMA) (° C.) Elastic modulus 28/24 28/24 26/22 (30/260° C.) (GPa) X/Y CTE (50-150° C.) 4 4 4 (ppm/° C.) Water absorption (%) 0.2 0.2 0.4 Peel strength 0.7 0.68 0.6 (kfg/cm)

(30) TABLE-US-00004 TABLE 4 Compar- Compar- Compar- Compar- ative ative ative ative Example 2 Example 3 Example 4 Example 5 Viscosity 50 40 40 500 (25° C., cps) Desmear 0.015 0.01 0.015 0.013 (g/50 cm.sup.2) Glass transition 300 280 300 290 temperature (DMA) (° C.) Glass transition 260 245 270 260 temperature (TMA) (° C.) Elastic modulus 27/23 26/22 28/24 22/19 (30/260° C.) (GPa) X/Y CTE (50-150° C.) 5 5 4 7 (ppm/° C.) Water absorption (%) 0.4 0.35 0.4 0.4 Peel strength 0.65 0.6 0.65 0.6 (kfg/cm)

(31) As shown in the results of Tables 3 and 4, in Examples of the present invention, benzoxazine resin was used at a content of 10 parts by weight or less based on 100 parts by weight of the binder, and the slurry type filler was used, such that dispersibility of the resin was improved as compared to Comparative Examples. Therefore, it may be confirmed that in the case of the present invention, more excellent chemical resistance and adhesion force, and high grass transition temperature may be implemented as compared to Comparative Examples.

(32) Although the present invention has been described in detail based on particular features thereof, and it is obvious to those skilled in the art that these specific technologies are merely preferable embodiments and thus the scope of the present invention is not limited to the embodiments. Therefore, the substantial scope of the present invention is defined by the accompanying claims and equivalent thereof.