CURABLE RESIN COMPOSITION

Abstract

A curable resin composition having fast-curing properties, high heat resistance, and excellent infiltration properties. The composition contains: a cyanate ester resin, an epoxy resin, a latent curing agent, and an inorganic pigment containing at least one metal selected from titanium, iron, copper, chromium, zirconium, calcium, manganese, and zinc. The inorganic pigment preferably has a primary particle size of 5 to 150 nm. The inorganic pigment is preferably present in an amount of 0.01 to 10 parts by mass per 100 parts by mass of the sum of the cyanate ester resin and the epoxy resin.

Claims

1. A curable resin composition comprising (A) a cyanate ester resin, (B) an epoxy resin, (C) a latent curing agent, and (D) an inorganic pigment containing at least one metal selected from titanium, iron, copper, chromium, zirconium, calcium, manganese, and zinc.

2. The curable resin composition according to claim 1, wherein the cyanate ester resin (A) is at least one member selected from the group consisting of a compound represented by formula (1):
[Chem. 1]
NC—O-A.sup.1-Y.sup.1-A.sup.2-O—CN  (1) wherein Y.sup.1 represents a divalent hydrocarbon group; and A.sup.1 and A.sup.2 each independently represent a phenylene group, a compound represented by formula (2): ##STR00003## wherein m represents an integer of 1 or greater; Y.sup.2 and Y.sup.3 each independently represent a divalent hydrocarbon group; and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a prepolymer of the compound represented by formula (1) and/or the compound represented by formula (2).

3. The curable resin composition according to claim 1, wherein Y.sup.1 in formula (1) and Y.sup.2 and Y.sup.3 in formula (2) is at least one member selected from groups represented by formulae (Y-1) through (Y-9): ##STR00004## wherein n represents an integer of 4 to 12; R.sup.7 and R.sup.8 each independently represent a hydrogen atom or a methyl group; and * represents a bond.

4. The curable resin composition according to claim 1, wherein the latent curing agent (C) is an active hydrogen-containing amine compound.

5. The curable resin composition according to claim 4, wherein the active hydrogen-containing amine compound is at least one member selected from (C-1) a modified amine obtained by the reaction between an amine compound having one or more active hydrogens and an epoxy compound, (C-2) a modified amine obtained by the reaction between an amine compound having one or more active hydrogens and an isocyanate compound, (C-3) a modified amine obtained by the reaction between an amine compound having one or more active hydrogens, an epoxy compound, and an isocyanate compound, and (C-4) a latent curing agent containing at least one modified amine selected from (C-1), (C-2), and (C-3) and a phenol resin.

6. The curable resin composition according to claim 1, wherein the inorganic pigment (D) is titanium black.

7. The curable resin composition according to claim 1, wherein the inorganic pigment (D) has a primary particle size of 5 to 150 nm.

8. The curable resin composition according to claim 1, wherein the epoxy resin (B) is present in an amount of 20 to 200 parts by mass per 100 parts by mass of the cyanate ester resin (A).

9. The curable resin composition according to claim 1, wherein the inorganic pigment (D) is present in an amount of 0.01 to 10 parts by mass per 100 parts by mass of the sum of the cyanate ester resin (A) and the epoxy resin (B).

10. A cured product obtained by curing the curable resin composition according to claim 1.

11. An underfill material comprising the curable resin composition according to claim 1.

12. The curable resin composition according to claim 2, wherein Y.sup.1 in formula (1) and Y.sup.2 and Y.sup.3 in formula (2) is at least one member selected from groups represented by formulae (Y-1) through (Y-9): ##STR00005## wherein n represents an integer of 4 to 12; R.sup.7 and R.sup.8 each independently represent a hydrogen atom or a methyl group; and * represents a bond.

13. The curable resin composition according to claim 2, wherein the latent curing agent (C) is an active hydrogen-containing amine compound.

14. The curable resin composition according to claim 3, wherein the latent curing agent (C) is an active hydrogen-containing amine compound.

15. The curable resin composition according to claim 2, wherein the inorganic pigment (D) is titanium black.

16. The curable resin composition according to claim 3, wherein the inorganic pigment (D) is titanium black.

17. The curable resin composition according to claim 4, wherein the inorganic pigment (D) is titanium black.

18. The curable resin composition according to claim 5, wherein the inorganic pigment (D) is titanium black.

19. The curable resin composition according to claim 2, wherein the inorganic pigment (D) has a primary particle size of 5 to 150 nm.

20. The curable resin composition according to claim 3, wherein the inorganic pigment (D) has a primary particle size of 5 to 150 nm.

Description

EXAMPLES

[0058] The invention will now be illustrated in greater detail with reference to Examples and Comparative Examples, but it should be understood that the invention is not deemed to be limited by these examples.

Preparation Example 1— Synthesis of Latent Curing Agent EH

[0059] In a flask, 201 g of 1,2-diaminopropane was placed and heated to 60° C. To the flask, 580 g of Adeka Resin EP-4100E (bisphenol A epoxy resin, from ADEKA CORPORATION; epoxy equiv. 190) was added in small portions so that the system temperature might be kept between 100° and 110° C. The epoxy equivalent of Adeka Resin EP-4100E per mole of 1,2-diaminopropane was 1.12. After completion of the addition of Adeka Resin EP-4100E, the reaction system temperature was elevated to 140° C., at which the reaction was continued for 1.5 hours to give a modified polyamine.

[0060] To 100 g of the resulting modified polyamine, 30 g of MP-800K (phenol resin from ASAHI YUKIZAI CORPORATION; softening point 100° C.) was added. The solvent was removed at 180° to 190° C. and 30 to 40 torr over a period of 1 hour to obtain latent curing agent EH.

Examples 1 to 4 and Comparative Examples 1 and 2

[0061] Materials shown in Table 1 below were mixed by stirring to prepare a curable resin composition. The composition was evaluated in terms of infiltration properties, glass transition temperature (Tg), and linear expansion coefficient (al). The formulations (parts by mass) and results of evaluation are shown in Table 1.

Infiltration Properties:

[0062] Two glass plates (50 mm×50 mm) were stacked with an offset of 10 mm with 100 μm-thick sealing tape interposed therebetween to make an infiltration testing device having a gap of 100 μm. The testing device was put horizontally and heated to 55° C., and 0.2 ml of the curable resin composition was placed on the offset portion of the lower glass plate. The testing device was left in a horizontal position, and the infiltration time, i.e., the time required for the curable resin composition to infiltrate into the gap to a length of 20 mm from the edge of the upper glass plate was recorded. The infiltration properties were graded on the following scale.

“good” The infiltration time was 300 seconds or shorter.
“fair” The infiltration time was longer than 300 seconds and shorter than 400 seconds.
“poor” The infiltration time was 400 seconds or longer.

Glass Transition Temperature (Tg):

[0063] The curable resin composition was cured by heating at 125° C. for 1 hour to make a test specimen. A linear thermal expansion curve was prepared using a TMA in accordance with JIS K7197. The Tg was determined from the inflection point on the curve.

Linear Expansion Coefficient α1:

[0064] The curable resin composition was cured by heating at 125° C. for 1 hour to make a test specimen. A linear thermal expansion curve was prepared using a TMA in accordance with JIS K7197, from which a linear expansion coefficient al was obtained.

TABLE-US-00001 TABLE 1 Example Compara. Example 1 2 3 4 1 2 Epoxy Resin EP-1 5.0 5.0 5.0 5.0 5.0 5.0 EP-2 4.0 4.0 4.0 4.0 4.0 4.0 EP-3 2.0 2.0 2.0 2.0 2.0 2.0 Cyanate Ester CYE 20.0 20.0 20.0 20.0 20.0 20.0 Resin Curing Agent EH 8.0 8.0 8.0 8.0 8.0 8.0 Filler silica 60.0 60.0 60.0 60.0 60.0 60.0 Blackening CB1 0.6 Agent CB2 1.2 P1 0.6 P2 1.0 P3 0.1 P4 0.6 Infiltration Properties good good good good poor poor α1 (ppm) 25 25 25 25 25 25 Tg (° C.) 140 140 140 140 140 140 EP-1: Bisphenol F epoxy resin, EP-4901E from ADEKA CORPORATION EP-2: Aminophenol epoxy resin, EP-3950S from ADEKA CORPORATION EP-3: Dicyclopentadiene epoxy resin, EP-4088S from ADEKA CORPORATION CYE: Bisphenol cyanate ester resin, LeCy from Lonza Silica: Commercially available silica powder CB1: Carbon black, #750B from Mitsubishi Carbon Black; primary particle size: 22 nm CB2: Carbon black, #30 from Mitsubishi Carbon Black; primary particle size: 30 nm P1: Titanium black, 13M from Mitsubishi Materials Electronic Chemicals; primary particle size: 75 nm P2: Titanium black, 13M-C from Mitsubishi Materials Electronic Chemicals; primary particle size: 97 nm P3: Titanium black, UF8 from Mitsubishi Materials Electronic Chemicals; primary particle size: 20 nm P4: Black shielding pigment, Tipaque Black SG-101 [(Ca, Ti, Mn)O.sub.3] from Ishihara Sangyo; average particle size: 950 nm

[0065] As shown in Table 1, the curable resin composition of the invention has excellent infiltration properties. In contrast, the resin compositions containing carbon black are inferior in infiltration properties.

INDUSTRIAL APPLICABILITY

[0066] The invention provides a curable resin composition that exhibits excellent infiltration properties and achieves fast curing to produce a highly heat-resistant cured product. Therefore, the curable resin composition is suited for use as an underfill material.