Active ester composition and cured product thereof

Abstract

Provided are an active ester composition capable of exhibiting high curability and forming a cured product with various excellent properties such as low dielectric properties, a cured product thereof, and a semiconductor encapsulating material and a printed wiring board which are obtained using the active ester composition. The active ester composition includes, as essential components, an active ester compound (A) and a phenolic hydroxyl group-containing compound (B), in which the active ester compound (A) is an esterification product of a compound having one phenolic hydroxyl group in the molecular structure (a1) and an aromatic polycarboxylic acid or an acid halide thereof (a2). Also provided are a cured product thereof, and a semiconductor encapsulating material and a printed wiring board which are obtained using the active ester composition.

Claims

1. An active ester composition comprising as essential components: an active ester compound (A) that is an esterification product of a compound having one phenolic hydroxyl group in a molecular structure (a1) and an aromatic polycarboxylic acid or an acid halide thereof (a2); and a phenolic hydroxyl group-containing compound (B), wherein the phenolic hydroxyl group-containing compound (B) is one or more selected from a phenolic hydroxyl group-containing monomer compound (B1), a novolac type resin that is a condensation reaction product of the phenolic hydroxyl group-containing monomer compound (B1) and an aldehyde compound and has a hydroxyl equivalent in the range of 100 to 250 g/eq, and a reaction product of raw materials including, as essential reactive raw materials, the phenolic hydroxyl group-containing monomer compound (B1) and a compound (x) represented by any one of the following Structural Formulae (x-1) to (x-5): ##STR00003## wherein h is 0 or 1; R.sup.2s each independently represent any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group; i is 0 or an integer of 1 to 4; Z represents any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxy methyl group; Y represents any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group; and j is an integer of 1 to 4, the reaction product having a hydroxyl equivalent in the range of 150 to 300 g/eq.

2. The active ester composition according to claim 1, wherein the active ester composition comprises 100 parts by mass of the active ester compound (A) and 0.1 to 300 parts by mass of the phenolic hydroxyl group-containing compound (B).

3. A curable composition comprising the active ester composition according to claim 1 and a curing agent.

4. A cured product comprising a product obtained by curing the curable composition according to claim 3.

5. A semiconductor encapsulating material comprising the curable composition according to claim 3.

6. A printed wiring board comprising a product obtained using the curable composition according to claim 3.

7. A curable composition comprising the active ester composition according to claim 2 and a curing agent.

8. A cured product comprising a product obtained by curing the curable composition according to claim 7.

9. A semiconductor encapsulating material comprising the curable composition according to claim 7.

10. A printed wiring board comprising a product obtained using the curable composition according to claim 7.

Description

EXAMPLES

(1) Next, the present invention will be described in more detail by way of Examples and Comparative Examples. The descriptions part and % in Examples are on the basis of the mass unless otherwise stated particularly.

(2) In this Example, the melt viscosity of the active ester compound (A) is a value at 150 C. which is measured according to ASTM D4287 with an ICI viscometer.

Production Example 1 Production of Active Ester Compound (A1)

(3) Into a flask equipped with a thermometer, a dropping funnel, a cooling pipe, a fractionating column, and a stirrer, 202.0 g of isophthalic acid chloride and 1250 g of toluene were charged, and the content was dissolved under reduced pressure in a system purged with nitrogen. Then, 288.0 g of 1-naphthol was charged, and the content was dissolved under reduced pressure in a system purged with nitrogen. 0.63 g of tetrabutylammonium bromide was added thereto under purging with nitrogen gas while the temperature inside the system was controlled to 60 C. or lower, and 400 g of a 20% sodium hydroxide aqueous solution was added dropwise thereto over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour without any changes to perform reaction. After the completion of the reaction, the reaction mixture was left to stand in order to separate into phases, and the water layer was removed. Water was added to the remaining organic layer and mixed and stirred for about 15 minutes, and then the mixture was left to stand in order to separate into phases, and the water layer was removed. This operation was repeated until the pH of the water layer reached 7. Thereafter, the moisture and toluene were removed by dehydration with a decanter to obtain an active ester compound (A1). The melt viscosity of the active ester compound (A1) was 0.6 dPa.Math.s.

Production Example 2 Production of Active Ester Compound (A-2)

(4) Into a flask equipped with a thermometer, a dropping funnel, a cooling pipe, a fractionating column, and a stirrer, 202.0 g of isophthalic acid chloride and 1400 g of toluene were charged, and the content was dissolved under reduced pressure in a system purged with nitrogen. Then, 340.0 g of orthophenyl phenol was charged, and the content was dissolved under reduced pressure in a system purged with nitrogen. 0.70 g of tetrabutylammonium bromide was added thereto under purging with nitrogen gas while the temperature inside the system was controlled to 60 C. or lower, and 400 g of a 20% sodium hydroxide aqueous solution was added dropwise thereto over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour without any changes to perform reaction. After the completion of the reaction, the reaction mixture was left to stand in order to separate into phases, and the water layer was removed. Water was added to the remaining organic layer and mixed and stirred for about 15 minutes, and then the mixture was left to stand in order to separate into phases, and the water layer was removed. This operation was repeated until the pH of the water layer reached 7. Thereafter, the moisture and toluene were removed by dehydration with a decanter to obtain an active ester compound (A-2). The melt viscosity of the active ester compound (A-2) was 0.2 dP.Math.s.

Examples 1 to 7 and Comparative Examples 1 and 2

(5) Each set of components were mixed in the proportions shown in Table 1 below to form a curable composition. As for the obtained curable composition, the gel time, and the dielectric constant of a cured product, and the elastic modulus of the cured product under high temperature conditions were measured in the following manner. The results are presented in Table 1.

Measurement of Gel Time

(6) Each set of components were mixed in proportions shown in Table 1 below to form a curable composition. Immediately thereafter, 0.15 g of the curable composition was placed on a hot plate heated to 175 C., and then the time taken for the curable composition to reach a gel state was measured while the composition was stirred with a spatula. The same operation was repeated three times, and the average value was used for evaluation.

(7) A: 10 seconds or longer and shorter than 50 seconds

(8) B: 50 seconds or longer and shorter than 100 seconds

(9) C: 100 seconds or longer and shorter than 150 seconds

(10) D: 150 seconds or longer

Measurement of Dielectric Constant

(11) The curable composition was poured into a mold and molded at a temperature of 175 C. for 10 minutes using a pressing machine. The molded product was taken out from the mold and then cured at a temperature of 175 C. for 5 hours. The cured molded product was cut into a size of 1 mm54 mm1.6 mm, and the resultant product was used as a test piece.

(12) After vacuum drying under heating, the dielectric constant and dielectric tangent at 1 GHz of the test piece stored in the room at 23 C. and a humidity of 50% for 24 hours were measured according to JIS-C-6481 using an impedance material analyzer HP4291B manufactured by Agilent Technologies.

(13) A: less than 3.00

(14) B: 3.00 or more

Measurement of Elastic Modulus Under High Temperature Condition

(15) The curable composition was poured into a mold and molded at a temperature of 175 C. for 10 minutes using a pressing machine. The molded product was taken out from the mold and then cured at a temperature of 175 C. for 5 hours. The cured molded product was cut into a size of 5 mm54 mm2.4 mm, and the resultant product was used as a test piece.

(16) The storage elastic modulus at 260 C. of the test piece was measured using a viscoelasticity measuring apparatus (solid viscoelasticity measuring apparatus RSAII manufactured by Rheometric Scientific Inc.) by a rectangular tension method under the conditions of a frequency of 1 Hz and a temperature raising rate of 3 C./min.

(17) A: 1 MPa or more and less than 25 MPa

(18) B: 25 MPa or more and less than 50 MPa

(19) C: 50 MPa or more

(20) TABLE-US-00002 TABLE 1 Example Example Example Example Example Example Example Comparative Comparative 1 2 3 4 5 6 7 Example 1 Example 2 Active ester [parts by 34.0 20.4 37.2 38.0 48.8 34.0 50.8 compound (A1) mass] Active ester [parts by 35.3 compound (A2) mass] Phenolic hydroxyl [parts by 2.0 group-containing mass] monomer compound (B1-1) Phenolic hydroxyl [parts by 11.2 20.4 11.7 11.2 34.0 group-containing resin mass] (B2-1) Phenolic hydroxyl [parts by 12.4 group-containing resin mass] (B2-2) Phenolic hydroxyl [parts by 12.7 group-containing resin mass] (B2-3) Epoxy resin (1) [parts by 54.8 59.2 50.4 49.3 49.2 53.0 54.8 66.0 49.2 mass] Triphenylphosphine [parts by 1.0 1.0 1.0 1.0 1.0 1.0 1.0 mass] 2-Phenylimidazole [parts by 1.0 1.0 mass] Gel time [sec] A A A B B A B A D Dielectric constant A A A A A A A B A Storage elastic [Mpa] A A A A A A A C A modulus at 260 C.

Details of Respective Components in Table

(21) Phenolic hydroxyl group-containing monomer compound (B1-1): pyrogallol

(22) Phenolic hydroxyl group-containing resin (B2-1): a phenol novolac resin (TD-2131 manufactured by DIC Corporation, hydroxyl equivalent of 104 g/eq, softening point of 80 C.)

(23) Phenolic hydroxyl group-containing resin (B2-2): a phenol aralkyl resin (HE100C-15 manufactured by AIR WATER INC., hydroxyl equivalent of 174 g/eq, softening point of 75 C.)

(24) Phenolic hydroxyl group-containing resin (B2-3): a biphenyl aralkyl resin (HE200C-10 manufactured by AIR WATER INC., hydroxyl equivalent of 204 g/eq, softening point of 72 C.)

(25) Epoxy resin (1): a cresol novolac type epoxy resin (N-655-EXP-S manufactured by DIC Corporation, epoxy equivalent of 202 g/eq)

Examples 8 to 14 and Comparative Example 3

(26) Respective components were mixed at a ratio presented in the following Table 2 to obtain a curable composition. Regarding the obtained curable composition, the moisture absorption resistance and the curing shrinkage percentage of the cured product were measured by the following manner. The results are presented in Table 2.

Evaluation of Moisture Absorption Resistance

(27) The curable composition was poured into a mold and molded at a temperature of 175 C. for 10 minutes using a pressing machine. The molded product was taken out from the mold and then cured at a temperature of 175 C. for 5 hours. The cured molded product was cut into a size of 90 mm110 mm2.4 mm, and the resultant product was used as a test piece.

(28) The obtained molded product was left to stand in an atmosphere of 85 C./85% RH for 300 hours, and then a moisture absorption test was performed. The mass of the molded product before and after the test was measured, and a mass change rate was evaluated as moisture absorptivity.

(29) A: less than 1% by mass

(30) B: 1% by mass or more

Measurement of Curing Shrinkage Percentage

(31) The curable composition was injection-molded using a transfer molding machine (KTS-15-1.5C manufactured by Kohtaki Precision Machine Co., Ltd.) under the conditions of a mold temperature of 154 C., a molding pressure of 9.8 MPa, and a curing time of 600 seconds to obtain a molded product having a length of 110 mm, a width of 12.7 mm, and a thickness of 1.6 mm. Then, the obtained molded product was cured at 175 C. for 5 hours, and then left to stand at room temperature (25 C.) for 24 hours, and the resultant product was used as a test piece. The size in the longitudinal direction of the test piece at room temperature and the inner size in the longitudinal direction of the mold at 154 C. were respectively measured and the curing shrinkage percentage was calculated by the following equation.

(32) Curing shrinkage percentage (%)={(the inner size in the longitudinal direction of the mold at 154 C.)(the size in the longitudinal direction of the test piece at room temperature)}/(the inner size in the longitudinal direction of the mold at 154 C.)100(%)

(33) A: less than 1%

(34) B: 1% or more

(35) TABLE-US-00003 TABLE 2 Example Example Example Example Example Example Example Comparative 8 9 10 11 12 13 14 Example 3 Active ester compound (A1) [parts by 34.0 20.4 37.2 38.0 48.8 34.0 mass] Active ester compound (A2) [parts by 35.3 mass] Phenolic hydroxyl group- [parts by 2.0 containing monomer compound mass] (B1-1) Phenolic hydroxyl group- [parts by 11.2 20.4 11.7 11.2 34.0 containing resin (B2-1) mass] Phenolic hydroxyl group- [parts by 12.4 containing resin (B2-2) mass] Phenolic hydroxyl group- [parts by 12.7 containing resin (B2-3) mass] Epoxy resin (1) [parts by 54.8 59.2 50.4 49.3 49.2 53.0 54.8 66.0 mass] Triphenylphosphine [parts by 1.0 1.0 1.0 1.0 1.0 1.0 1.0 mass] 2-Phenylimidazole [parts by 1.0 mass] Fused silica [parts by 100 100 100 100 100 100 100 100 mass] Silane coupling agent [parts by 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 mass] Carnauba wax [parts by 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 mass] Moisture absorptivity [% by A A A A A A A B mass] Curing shrinkage percentage [%] A A A A A A A B