RESIN COMPOSITION

Abstract

A resin composition including (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, in which a chloride ion content included in the resin composition measured in accordance with a sample combustion ion chromatography method (BS EN 14532 2007) is 50 ppm or less.

Claims

1. A method for producing a resin composition, the method comprising: mixing an epoxy resin from which epichlorohydrin has been removed via distillation, (B) a curing agent, and (C) an inorganic filler; wherein a chloride ion content included in the resin composition measured in accordance with a sample combustion ion chromatography method (BS EN 14582 2007) is 50 ppm or less.

2. The method according to claim 1, wherein a content of (C) the inorganic filler in the resin composition is 80% or more by mass when non-volatile components in the resin composition is taken as 100% by mass.

3. The method according to claim 1, wherein coefficient of thermal expansion of a cured product obtained by thermally curing the resin composition at 180° C. for 90 minutes is 15 ppm or less.

4. The method according to claim 1, wherein (B) the curing agent comprises an acid anhydride curing agent.

5. The method according to claim 1, wherein the resin composition is in a liquid state.

6. The method according to claim 1, wherein said (A) component comprises at least one selected from the group consisting of a bisphenol A epoxy resin and a bisphenol F epoxy resin.

7. The method according to claim 1, wherein said (A) component comprises a glycidyl amine epoxy resin.

8. The method according to claim 1, wherein a lowest melt viscosity of the resin composition is 50 poise or more and 4,000 poise or less.

9. The method according to claim 1, wherein a content of a solvent is 1% or less by mass when the entire resin composition is taken as 100% by mass.

10. The method according to claim 1, wherein a weight-average molecular weight of said (A) component is 100 to 5000.

11. The method according to claim 1, wherein a content of said (A) component in the resin composition is 1% or more by mass and 20% or less by mass when non-volatile components in the resin composition is taken as 100% by mass.

12. The method according to claim 1, wherein a particle diameter of said (C) component is 0.1 μm or more and 20 μm or less.

13. The method according to claim 1, wherein said component comprises: at least one selected from the croup consisting of a bisphenol A epoxy resin and a biaphenol F epoxy resin, and a glycidyl amine epoxy resin.

14. The method according to claim 1, wherein said (A) component comprises at least one selected from the group consisting of a bispnenol A epoxy resin and a bisphenol F epoxy resin, and a glycidyl amine epoxy resin, wherein a content of (C) the inorganic filler in the resin composition is 80% or more by mass, when non-volatile components in the resin composition is taken as 100% by mass.

15. The method according to claim 1, wherein said (A) component comprises at least one selected from the group consisting of a bisphenol A epoxy resin and a bisphenol F epoxy resin, and a glycidyl amine epoxy resin, wherein a content of (C) the inorganic filler in the resin composition is 80% or more by mass when non-volatile components in the resin composition is taken as 100% by mass, wherein the resin composition is in a liquid state.

16. The method according to claim 1, wherein said (A) component comprises at least one selected from the group consisting of a bisphenol A epoxy resin and a bisphenol F epoxy resin, and a glycidyl amine epoxy resin, wherein a content of (C) the inorganic filler in the resin composition is 80% or more by mass when non-volatile components in the resin composition is taken as 100% by mass, wherein the resin composition is in a liquid state, wherein (B) the curing agent comprises an acid anhydride curing agent.

17. The method according to claim 1, wherein the resin composition is used for sealing the semiconductor chip.

18. The method according to claim 1, wherein the resin composition is used for sealing the semiconductor chip in Fan-out type WLP.

Description

EXAMPLES

[0157] Hereinafter, the present invention will be explained specifically by means of Examples. It must be noted here that the present invention is not limited to Examples described below. In the explanation below, “ppm”, “parts”, and “%”, which express quantities, are on the mass basis unless otherwise specifically mentioned. The operations explained hereinafter were carried out under normal temperature and normal pressure unless otherwise specifically mentioned.

[0158] The epoxy resin used in Examples were used after the commercially purchased resin was purified by distillation. Silica A, Silica B, and Silica C used in Examples and Comparative Example are as follows. [0159] Silica A: average particle diameter of 9.2 μm and specific surface area of 3.3 m.sup.2/g, surface of which is treated with KBM 573 (N-phenyl-3-aminopropyl trimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ld.). [0160] Silica B: average particle diameter of 8.5 μm and specific surface area of 3.2 m.sup.2/g, surface of which is treated with KBM 403 (3-glycidoxypropyl trimethoxy silane, manufactured by Shin-Etsu Chemical Co., Ld.). [0161] Silica C: average particle diameter of 5.6 μm and specific surface area of 2.8 m.sup.2/g, surface of which is treated with KBM 4803 (long chain epoxy type silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ld.).

Example 1

[0162] A mixture of 5 parts of a glycidyl amine type epoxy resin (epoxy equivalent of 95 g/eq.), 5 parts of a bisphenol type epoxy resin (1:1 mixture of bisphenol A type and bisphenol F type; epoxy equivalent of 169 g/eq.), 7 parts of an acid anhydride curing agent (“MH-700”; acid anhydride equivalent of 164 g/eq., manufactured by New Japan Chemical Co., Ltd.), 140 parts of Silica A, 0.1 part of a curing accelerator (“1B2PZ”: 1-benzyl-2-phenyl imidazole, manufacture by Shikoku Chemicals Corp.), and 0.6 part of carbon black (“MA-600MJ-S”, manufactured by Mitsubishi Chemical Corp.) was uniformly dispersed by means of a mixer to obtain Resin Composition 1.

Example 2

[0163] In Example 1, Silica A was replaced by Silica B. Resin Composition 2 was, prepared in the same manner as Example 1 except for this change.

Example 3

[0164] In Example 1, Silica A was replaced by Silica C. Resin Composition 3 was prepared in the same manner as Example 1 except for this change.

Example 4

[0165] In Example 1, 3 parts of an alicyclic epoxy resin (epoxy equivalent of 136 g/eg.) was additionally used. Resin Composition 4 was prepared in the same manner as Example 1 except for this change.

Comparative Example 1

[0166] In Example 1,

[0167] 5 parts of the glycidyl amine type epoxy resin (epoxy equivalent of 95 g/eq.) was changed to 5 parts of the clycidyl amine type epoxy resin (“630”: epoxy equivalent of 95 g/eq., manufactured by Mitsubishi Chemical Corp.), and

[0168] 5 parts of the bisphenol type epoxy resin (1:1 mixture of bisphenol A type and bisphenol F type; epoxy equivalent of 169 g/eq.) was changed to 5 parts of bisphenol F type epoxy (“EX-211”: epoxy equivalent of 138 g/eq., manufactured by Nagase ChemteX Corp.).

[0169] Resin Composition 5 was prepared in the same manner as Example 1 except for these changes. In Comparative Example 1, commercially purchased “630” and “EX-211” were used as they were without being distilled.

<Measurement of Chloride Ion Content>

[0170] The chloride ion contents of Resin Compositions 1 to 5 prepared in Examples 1 to 5 and Comparative Example 1 were measurer) with a sample combustion ion chromatography method (in accordance with BS EN 14532 2007).

<Measurement of Coefficient of Thermal Expansion (CTE)>

[0171] Resin Compositions 1 to 5 each prepared in Examples and Comparative Example was compression molded onto a release-treated 12-inch silicon wafer by using a compression molding apparatus (mold temperature of 130° C., pressure of 6 MPa, and curing period of 10 minutes) to obtain the resin composition layer having thickness of 300 μm. Then, the resin composition layer was removed from the release-treated silicon wafer, and then, the resin composition layer was thermally cured by heating at 180° C. for 90 minutes to obtain a cured sample. The cured sample was cut to the width of 5 mm and the length of 15 mm to obtain a specimen. This specimen was subjected to a thermal mechanical analysis with a tensile load method by using a thermal mechanical analysis apparatus (“ThermoPlus TMA8310, manufactured by Rigaku Corp.). Specifically, after the specimen was attached to the thermal mechanical analysis apparatus, it was continuously measured twice with the load of 1 g and the temperature raising rate of 5° C./minute as the measurement conditions. In the second measurement, the coefficient of thermal expansion (ppm/° C.) in a plane direction in the temperature range of 25 to 150° C. was calculated.

<Measurement of Lowest Melt Viscosity>

[0172] The lowest melt viscosity of Resin Compositions 1 to 5 each prepared in Examples and Comparative Example was measured by using a dynamic viscoelasticity measurement apparatus (“Rheozol-G3000”, manufactured by UBM Co., Ltd.). The dynamic viscoelasticity of 1 g of the resin composition sample was measured by using parallel plates having the diameter of 18 mm with the temperature raising rate of 5° C./minute from the measurement start temperature of 60° C. till 200° C. and with the measurement temperature interval of 2.5° C., oscillation of 1 Hz, and distortion of 1 deg. as the measurement conditions to obtain the value of the lowest melt viscosity.

<Evaluation of Copper Adhesion after HAST Test>

[0173] The specimen of the resin composition, each prepared in Examples and Comparative Example, having the diameter of 4 mm and the thickness of 5 mm was prepared on the copper plane of a glass cloth based epoxy resin double-sided copper-cladded laminate (“R1515A”: copper foil having the thickness of 18 μm and substrate having the thickness of 0.4 mm, manufactured by Panasonic Corp.). Specifically, the resin composition was filled in a silicon rubber frame having the height or 4 mm obtained by hollowing out the silicon rubber so as to give a column shape having the height of 5 mm; then, after it was heated at 180° C. for 90 minutes, the silicon rubber frame was removed to obtain the specimen. After the specimen was subjected to the high temperature and high humidity environmental test (HAST) at 130° C. and 85% RH for 96 hours, the shear strength of the interface between the copper and the specimen in the position where the head position is 1 mm from the substrate by using a bond tester (series 4000, manufactured by Dage Corp.) with the head speed of 700 μm/s. The test was repeated for 5 times, and the average value thereof was obtained. When the shear strength was 0.5 kgf/mm.sup.2 or more, it is marked by O, and when the shear strength was less than 0.5 kgf/mm.sup.2, it is marked by x.

TABLE-US-00001 TABLE 1 Comparative Example Example 1 2 3 4 1 (A) Component Glycidyl amine epoxy resin 5 5 5 5 Bisphenol epoxy resin 5 5 5 2 Alicyclic epoxy resin 3 630 5 EX-211 5 (B) Component MH-700 7 7 7 7 7 (C) Component Silica A 140 140 140 Silica B 140 Silica C 140 (D) Component 1B2PZ 0.1 0.1 0.1 01 0.1 (E) Component MA-600MJ-S 0.6 0.6 0.6 0.6 0.6 Total of non-volatile components 157.7 157.7 157.7 157.7 157.7 Chloride on content (ppm) 19 20 19 10 110 Coefficient of thermal expansion (ppm/.Math.C) 7.40 8.10 6.60 7.00 10.00 Lowest melt viscosity (poise) 230 300 350 230 370 Adhesion after HAST ∘ ∘ ∘ ∘ x

[0174] In Examples 1 to 4, even in the case that the (D) to (E) components were absent, it was confirmed that similar results to those in Examples described above could be obtained, although the results are different to some extent.