THERMOSETTING RESIN COMPOSITE AND METAL CLAD LAMINATE USING THE SAME

Abstract

The present disclosure relates to a thermosetting resin composite having a specific thermal stress factor, and capable of implementing a low glass transition temperature, low modulus, and a low coefficient of thermal expansion, and minimizing warpage, and having excellent flowability in a prepreg or semi-cured state, and a metal clad laminate using the same.

Claims

1. A thermosetting resin composite for a metal clad laminate, having a thermal stress factor of 25 Mpa or less calculated by the following General Formula 1:
Thermal Stress Factor [(Storage Modulus)CTE]dT [General Formula 1] in General Formula 1, the thermal stress factor is calculated from the storage modulus and the CTE (coefficient of thermal expansion) measured at a temperature range of 30 C. to 260 C., respectively.

2. The thermosetting resin composite for a metal clad laminate of claim 1, wherein the thermosetting resin composite has the thermal stress factor in the range of 10 to 25 MPa.

3. The thermosetting resin composite for a metal clad laminate of claim 1, wherein the thermosetting resin composite comprises a thermosetting resin composition and a fabric substrate.

4. The thermosetting resin composite for a metal clad laminate of claim 3, wherein the thermosetting resin composition comprises: an amine compound containing one or more of at least one kind of functional group selected from the group consisting of a sulfone group; a carbonyl group; a halogen group; a Cl to C20 alkyl group unsubstituted or substituted with a nitro group, a cyano group or a halogen group; a C6 to C20 aryl group unsubstituted or substituted with a nitro group, a cyano group or a halogen group; a C2 to C30 heteroaryl group unsubstituted or substituted with a nitro group, a cyano group or a halogen group; and a C1 to C20 alkylene group unsubstituted or substituted with a nitro group, a cyano group or a halogen group, a thermosetting resin, a thermoplastic resin, and an inorganic filler.

5. The thermosetting resin composite for a metal clad laminate of claim 3, wherein the thermosetting resin composition has a glass transition temperature of 230 C. or less.

6. The thermosetting resin composite for a metal clad laminate of claim 4, wherein the thermosetting resin composition comprises the thermosetting resin in an amount of 400 parts by weight or less based on 100 parts by weight of the amine compound.

7. The thermosetting resin composite for a metal clad laminate of claim 4, wherein the thermosetting resin composition has an equivalent ratio of 1.4 or more calculated by the following Equation 1:
Equivalent ratio=total active hydrogen equivalent contained in the amine compound/total curable functional group equivalent contained in the thermosetting resin. [Equation 1]

8. The thermosetting resin composite for a metal clad laminate of claim 4, wherein the amine compound comprises an aromatic amine compound containing 2 to 5 amine groups.

9. The thermosetting resin composite for a metal clad laminate of claim 4, wherein the thermosetting resin composition comprises 50 to 150 parts by weight of the inorganic filler based on 100 parts by weight of a total amount of the thermosetting resin, the thermoplastic resin and the amine compound.

10. The thermosetting resin composite for a metal clad laminate of claim 4, wherein the inorganic filler comprises two or more kinds of inorganic fillers having different average particle diameters, and at least one of the two or more kinds of inorganic fillers is an inorganic filler having an average particle diameter of 0.1 m to 100 m, and at least one other is an inorganic filler having an average particle diameter of 1 nm to 90 nm.

11. The thermosetting resin composite for a metal clad laminate of claim 1, wherein the thermosetting resin composite has the storage modulus of 16 GPa or less at 30 C. and 180 C., respectively.

12. The thermosetting resin composite for a metal clad laminate of claim 11, wherein the thermosetting resin composite has the storage modulus of 8 Gpa or less at 260 C.

13. The thermosetting resin composite for a metal clad laminate of claim 1, wherein the thermosetting resin composite has the CTE of 5 to 12 ppm/ C.

14. A metal clad laminate, comprising the thermosetting resin composite of claim 1; and a metal foil formed on at least one surface of the thermosetting resin composite.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0128] Hereinafter, the present invention will be explained in detail with reference to the following examples. However, these examples are only to illustrate the invention, and the scope of the invention is not limited thereto.

Examples and Comparative Examples: Thermosetting Resin Composition for Semiconductor Package, Prepreg, Thermosetting Resin Composite for Metal Clad Laminate and Copper Clad Laminate

[0129] (1) Preparation of Thermosetting Resin Composition for Semiconductor Package

[0130] Components were mixed in methyl ethyl ketone at a solid content of 40% so as to have compositions as shown in the following Tables 1 and 2, and stirred at 400 rpm for one day at room temperature to obtain resin compositions (resin varnish) for a semiconductor package of Examples and Comparative

[0131] Examples. Specifically, the specific composition of the resin composition prepared in the above Example is as shown in Table 1 below, and the specific composition of the resin composition prepared in the Comparative Example is as shown in Table 2 below.

[0132] (2) Preparation of Prepreg, Thermosetting Resin Composite for Metal Clad Laminate and Copper Clad Laminate

[0133] The resin composition (resin varnish) for a semiconductor package was impregnated into a glass fabric (T-glass #1010, manufactured by Nittobo) having a thickness of 13 m and then hot-air-dried at a temperature of 170 C. for 2 to 5 minutes, thereby preparing a prepreg.

[0134] After two sheets of the prepregs prepared as described above were laminated, a copper foil (thickness: 12 m, manufactured by Mitsui) was positioned and laminated on both surfaces thereof and cured at a temperature of 220 C. and a pressure of 35 kg/cm.sup.2 for 100 minutes, thereby preparing a copper clad laminate.

[0135] Experimental Examples: Measurement of Physical Properties of Thermosetting Resin Composition for Semiconductor Package, Prepreg, Thermosetting Resin Composite for Metal Clad Laminate and Copper Clad Laminate Obtained in Examples and Comparative Examples

[0136] Physical properties of the thermosetting resin compositions, prepregs, thermosetting resin composites for a metal clad laminate, and copper clad laminates obtained in Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3 below.

[0137] 1. Coefficient of Thermal Expansion (CTE)

[0138] The copper foil layer of the copper clad laminate obtained in the above Examples and Comparative Examples was removed by etching and then a test piece was prepared in a MD direction. Thereafter, a coefficient of thermal expansion (CTE) was measured from 30 C. to 260 C. at a heating rate of 10 C./min using TMA (manufactured by TA Instruments, Q400). The measured values in the range of 50 C. to 150 C. were listed as CTE.

[0139] Herein, a product obtained by etching a copper foil layer of a copper clad laminate may be referred to as a thermosetting resin composite for a metal clad laminate, and this is formed by curing a prepreg obtained by hot-air drying a thermosetting resin composition at a high temperature.

[0140] 2. Glass Transition Temperature (Tg)

[0141] The copper foil layer of the copper clad laminate obtained in the above Examples and Comparative Examples was removed by etching and then a test piece (a thermosetting resin composite for a metal clad laminate) was prepared in a MD direction. Thereafter, a glass transition temperature (Tg) was measured from 25 C. to 300 C. at a heating rate of 5 C./min in a tensile mode using DMA (manufactured by TA Instruments, Q800). A peak temperature of tan delta was determined as Tg.

[0142] 3. Measurement of Storage Modulus

[0143] The copper foil layer of the copper clad laminate obtained in the above Examples and Comparative Examples was removed by etching and then a test piece (a thermosetting resin composite for a metal clad laminate) was prepared in a MD direction. Thereafter, storage modulus was measured from 25 C. to 300 C. at a heating rate of 5 C./min in a tensile mode using DMA (manufactured by TA Instruments, Q800).

[0144] 4. Fillability of Circuit Pattern

[0145] The prepreg obtained in the above Examples and Comparative Examples was placed on both sides of a circuit pattern (pattern height: 7 m, residual rate: 50%), and a copper foil (thickness: 12 m, manufactured by Mitsui) was placed thereon. This was pressed for 100 minutes under conditions of 220 C. and 35 kg/cm.sup.2, followed by etching the copper foil on both sides to evaluate fillability of the circuit pattern under the following criteria.

[0146] : No void occurred

[0147] : Void occurred

[0148] 5. Measurement of Tensile Elongation

[0149] 15 sheets of the prepregs obtained in the above Examples and

[0150] Comparative Examples were laminated so as to the MD direction and the TD direction of the glass fabric coincided with each other. This was pressed for 100 minutes under conditions of 220 C. and 35 kg/cm.sup.2, followed by measuring the tensile elongation in the MD direction using Universal Testing Machine (manufactured by Instron 3365) in accordance with IPC-TM-650 (2.4.18.3).

[0151] 6. Measurment of Warpage of Semiconductor Package

[0152] A part of the copper foil of the copper clad laminate obtained in the above Examples and Comparative Examples was processed by a conventional etching method to prepare a printed circuit board (thickness: 90 m). A semiconductor package (14.5 mm14.5 mm390 m (thickness)) was manufactured by mounting a semiconductor chip (11.5 mm11.5 mm80 m (thickness)) on the prepared printed circuit board. The warpage was measured on the basis of Shadow Moire measurement theory using a warpage measuring device (manufactured by AKROMETRIX, THERMOIRE PS100) for the manufactured semiconductor package. The warpage was measured for the semiconductor package from 30 C. to 260 C. and then cooled to 30 C. The difference between the maximum value and the minimum value was calculated, and the warpage of the semiconductor package was evaluated under the following criteria.

[0153] : The difference between the maximum value and the minimum value of warpage is 170 m or less

[0154] : The difference between the maximum value and the minimum value of warpage is larger than 170 m

[0155] 7. Calculation of Thermal Stress Factor

[0156] The thermal stress factor of the following General Formula 1 was calculated by integrating the product of the CTE (coefficient of thermal expansion) and the storage modulus at every 1 C. from 30 C. to 260 C.

Thermal Stress Factor (unit: MPa) [(Storage Modulus)CTE]dT [General Formula 1]

TABLE-US-00001 TABLE 1 Compositions of thermosetting resin composition (unit: g) and physical properties of thermosetting resin composite for metal clad laminate, for Examples Ex. 1 Ex. 2 Ex. 3 Ex. 4 Epoxy resin XD-1000 0 14 0 (epoxy equivalent weight: 253 g/eq) NC-3000H (epoxy equivalent weight: 46.1 39.48 33.5 12 290 g/eq) HP-6000 (epoxy equivalent weight: 24 250 g/eq) Bismaleimide BMI-2300 (maleimide equivalent 4.3 3.72 4.3 3.72 weight: 179 g/eq) DDS 19.6 16.8 18.2 10.14 (active hydrogen equivalent weight: 62 g/eq) TFB 10.14 (active hydrogen equivalent weight: 80 g/eq) DDM (active hydrogen equivalent weight: 49.5 g/eq) Thermoplastic Acrylic rubber B (KG-3015P, Mw 30 30 resin 800,000) Acrylic rubber C (KG-3113, Mw 40 40 600,000) Inorganic filler SC2050MTO 70 90 108 135 AC4130Y 0 10 12 15 Equivalent ratio (diamine/epoxy) 1.73 1.73 1.51 1.84 Tg C. 212 209 221 197 CTE ppm/ C. 9.1 8.5 8.1 7.8 Fillability of circuit pattern Storage 30 C. Gpa 13.1 14.5 15.1 15.4 modulus 180 C. Gpa 9.7 11.2 11.6 11.8 260 C. Gpa 6.4 6.6 6.8 6.4 Tensile % 4.1 3.9 3.8 3.6 elongation TSF MPa 17.3 20.4 20.4 20.2 Warpage m

TABLE-US-00002 TABLE 2 Compositions of thermosetting resin composition (unit: g) and physical properties of thermosetting resin composite for metal clad laminate, for Comparative Examples Comp. Ex. Comp. Comp. Comp. 1 Ex. 2 Ex. 3 Ex. 4 Epoxy resin XD-1000 14.0 0 0 (epoxy equivalent weight: 253 g/eq) NC-3000H (epoxy equivalent weight: 65.8 65.8 65.8 290 g/eq) HP-6000 (epoxy equivalent weight: 28.0 250 g/eq) Bismaleimide BMI-2300 (maleimide equivalent 6.2 16.8 6.2 6.2 weight: 179 g/eq) DDS 11.2 28 28 (active hydrogen equivalent weight: 62 g/eq) TFB (active hydrogen equivalent weight: 80 g/eq) DDM (active hydrogen equivalent 28 weight: 49.5 g/eq) Thermoplastic Acrylic rubber B (KG-3015P, Mw 30 resin 800,000) Acrylic rubber C (KG-3113, Mw 600,000) Inorganic filler SC2050MTO 260 135 260 135 AC4130Y 0 15 0 15 Equivalent ratio (diamine/epoxy) 2.16 0.69 1.73 1.73 Tg C. 195 289 213 215 CTE ppm/ C. 9.8 7.8 9.6 11.6 Fillability of circuit pattern X Storage 30 C. Gpa 21.7 16.1 21.3 18.3 modulus 180 C. Gpa 18.2 15 19.2 16.6 260 C. Gpa 7.9 13.1 8.1 7 Tensile % 2.4 3.1 2.6 3 elongation TSF Mpa 40.3 28.5 39.6 41.2 Warpage m Inability to X X X manufacture a substrate due to poor moldability

[0157] DDS: 4,4-diaminodiphenyl sulfone

[0158] TFB: 2,2-bis(trifluoromethyl)benzidine

[0159] DDM: 4,4-diaminodiphenyl methane

[0160] XD-1000: Epoxy resin (manufactured by Nippon kayaku)

[0161] NC-3000H: Epoxy resin (manufactured by Nippon kayaku)

[0162] HP-6000: Epoxy resin (manufactured by DIC)

[0163] BMI-2300: Bismaleimide-based resin (manufactured by DAIWA KASEI)

[0164] Acrylic rubber B (Mw 800,000): PARACRON KG-3015P (manufactured by Negami chemical industrial Co.,LTD)

[0165] Acrylic rubber C (Mw 600,000): PARACRON KG-3113 (manufactured by Negami chemical industrial Co.,LTD)

[0166] Equivalent ratio: Calculated by the following Equation 1

Equivalent ratio of amine compound to thermosetting resin=(total active hydrogen equivalent of DDS+total active hydrogen equivalent of TFB+total active hydrogen equivalent of DDM)/{(total epoxy equivalent of XD-1000+total epoxy equivalent of NC-3000H +total epoxy equivalent of HP-6000) +(total maleimide equivalent of BMI-2300)}[Equation 1]

[0167] In Equation 1, the total active hydrogen equivalent of DDS is a value obtained by dividing a total weight of DDS (unit: g) by active hydrogen equivalent weight of DDS (62 g/eq).

[0168] The total active hydrogen equivalent of TFB is a value obtained by dividing a total weight of TFB (unit: g) by active hydrogen equivalent weight of TFB (80 g/eq).

[0169] The total active hydrogen equivalent of DDM is a value obtained by dividing a total weight of DDM (unit: g) by active hydrogen equivalent weight of DDM (49.5 g/eq).

[0170] The total epoxy equivalent of XD-1000 is a value obtained by dividing a total weight of XD-1000 (unit: g) by epoxy equivalent weight of XD-1000 (253 g/eq).

[0171] The total epoxy equivalent of NC-3000H is a value obtained by dividing a total weight of NC-3000H (unit: g) by epoxy equivalent weight of NC-3000H (290 g/eq).

[0172] The total epoxy equivalent of HP-6000 is a value obtained by dividing a total weight of HP-6000 (unit: g) by epoxy equivalent weight of HP-6000 (250 g/eq).

[0173] The total maleimide equivalent of BMI-2300 is a value obtained by dividing a total weight of BMI-2300 (unit: g) by maleimide equivalent weight of BMI-2300 (179 g/eq).

[0174] As shown in Table 1, it was confirmed that the thermosetting resin composite for a metal clad laminate obtained from the prepreg including an amine compound containing an electron withdrawing group (EWG) of Examples had excellent fillability of circuit pattern as well as a glass transition temperature of 230 C. or less and low CTE of 10 ppm/ C. or less.

[0175] That is, it was confirmed that the resin composition of Examples including the thermosetting resin in an amount of 290 parts by weight or less based on 100 parts by weight of the amine compound containing an electron withdrawing group (EWG) and the inorganic filler in an amount of 50 to 150 parts by weight based on 100 parts by weight of a total amount of the thermosetting resin, the thermoplastic resin and the amine compound, wherein the equivalent ratio of amine compound to thermosetting resin is 1.4 or more, could achieve thermal properties, excellent low thermal expansion characteristics, flowability and mechanical properties suitable for a semiconductor package.

[0176] In the meantime, it was confirmed that each thermosetting resin composite for a metal clad laminate obtained in Examples had a thermal stress factor of 21 MPa or less, and a semiconductor package manufactured using the thermosetting resin composite for a metal clad laminate having such a thermal stress factor exhibited relatively low warpage.

[0177] On the contrary, it was confirmed that each thermosetting resin composite for a metal clad laminate obtained in Comparative Examples had a thermal stress factor exceeding 25 Mpa, and a semiconductor package manufactured using the thermosetting resin composite for a metal clad laminate having such a high thermal stress factor exhibited relatively high warpage.