Addition-curable silicone resin composition, addition-curable silicone resin cured product, and sealed optical semiconductor element

Abstract

The invention aims to provide an addition curable silicone resin composition with excellent interfacial adhesion properties, storage stability and transparency. The addition curable silicone resin mixtures has a refractive index of 1.35 to 1.45 and includes a silicone compound having at least one group of the following formula: ##STR00001##

Claims

1. An addition-curable silicone resin composition comprising: an addition-curable silicone resin mixture; and an adhesion-imparting agent, the addition-curable silicone resin mixture having a refractive index of 135 to 1.45, the adhesion-imparting agent including a compound that includes a structural unit represented by the formula (1-3) and/or a structural unit represented by the formula (1-4) between a structural unit represented by the formula (1-1) and a structural unit represented by the formula (1-2), the compound having a refractive index of 1.35 to 1.45: ##STR00008## wherein R.sup.1a's in the formulas (1-1) and (1-2) each independently represent a C1-C18 alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; R.sup.1b's in the formulas (1-3) and (1-4) each independently represent a C1-C18 alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group; m in the formula (1-3) is an integer of 1 to 50; n in the formula (1-4) is an integer of 1 to 1500; and A's in the formulas (1-1) to (1-3) each independently represent a C1-C18 alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a group represented by the formula (2), provided that at least one of A's in the formulas (1-1) to (1-3) is a group represented by the formula (2): ##STR00009## wherein R.sup.2a represents a C1-C8 alkylene group in which a carbon atom other than a carbon atom bonded to a silicon atom is optionally partially substituted with an oxygen atom; R.sup.2b's each independently represent a C1-C3 alkylene group; R.sub.3's each independently represent a C1-C3 alkylene group; R.sup.4's each independently represent a hydrogen atom, a C1-C3 alkyl group, an OH group-containing C1-C3 alkyl group, or a halogeno group; and x is an integer of 0 to 2.

2. The addition-curable silicone resin composition according to claim 1, wherein, in the formula (2), R.sup.3 represents methylene and R.sup.4's each independently represent a hydrogen atom or hydroxymethyl.

3. The addition-curable silicone resin composition according to claim 1, wherein the adhesion-imparting agent is contained in an amount of 0.01% to 15% by mass.

4. The addition-curable silicone resin composition according to claim 1, wherein the addition-curable silicone resin mixture comprises a polyorganosiloxane having at least two substituents each containing a carbon-carbon double bond that is bonded to a silicon atom, a polyorganohydrogensiloxane having at least two hydrogen atoms each bonded to a silicon atom, and a hydrosilylation reaction catalyst.

5. The addition-curable silicone resin composition according to claim 1, wherein the substituents each containing a carbon-carbon double bond that is bonded to a silicon atom, in the polyorganosiloxane, are vinyl.

6. An addition-curable silicone resin cured product prepared by curing the addition-curable silicone resin composition according to claim 1.

7. A sealed optical semiconductor element in which an optical semiconductor device is sealed with the addition-curable silicone resin cured product according to claim 6.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1A to 1C are schematic views showing failure patterns in cases where various addition-curable silicone resin compositions are used to bond adherends.

DESCRIPTION OF EMBODIMENTS

(2) The present invention is explained in more detail below based on examples, but is not limited to these examples.

Production Example 1

Reaction of Amino Group-Containing Silicone Compound with Ethylene Carbonate (Preparation of Adhesion-Imparting Agent A)

(3) A 50-mL four-necked flask equipped with a magnetic stir bar, a thermometer, and a condenser was charged under a nitrogen atmosphere with 10.0 g (amino group 2.00 mmol) of an amino group-containing silicone compound (“KF-865” produced by Shin-Etsu Chemical Co., Ltd., amino group equivalent 5,000 g/mol) and 0.35 g (4.00 mmol) of ethylene carbonate (molecular weight 88.06). The contents were heated to 120° C. and stirred using a magnetic stirrer for 15 hours. The remaining amino groups were confirmed to be less than 1% by neutralization titration. Then, the reaction solution was transferred to a 200-mL four-necked flask equipped with a stirrer, a thermometer, and a condenser. To the solution were added 50 g of chlorobenzene and 50 g of water, and phase separation was performed. The organic phase was condensed to give 9.3 g of a transparent liquid (adhesion-imparting agent A).

(4) Measurement of the adhesion-imparting agent A by .sup.1H-NMR confirmed that the adhesion-imparting agent A included a structural unit represented by the formula (1-1) (R.sup.1a is methyl, A is methyl), a structural unit represented by the formula (1-2) (R.sup.1a is methyl, A is methyl), a structural unit represented by the formula (1-3) (R.sup.1b is methyl, A is a group represented by the formula (2), R.sup.2a is n-propylene, x is 0, R.sup.3 is methylene, R.sup.4 is hydrogen), and a structural unit represented by the formula (1-4) (R.sup.1b is methyl).

(5) The refractive index of the adhesion-imparting agent A was measured to be 1.407 using a digital Abbe refractometer (produced by ATAGO CO., LTD.) under the conditions of 25° C. and a wavelength of 589 nm.

Production Example 2

Reaction of Amino Group-Containing Silicone Compound with Glycerol Carbonate (Preparation of Adhesion-Imparting Agent B)

(6) A 50-mL four-necked flask equipped with a magnetic stir bar, a thermometer, and a condenser was charged under a nitrogen atmosphere with 10.0 g (amino group 2.00 mmol) of an amino group-containing silicone compound (“KF-865” produced by Shin-Etsu Chemical Co., Ltd., amino group equivalent 5,000 g/mol) and 0.47 g (3.95 mmol) of glycerol carbonate (molecular weight 118.09). The contents were heated to 120° C. and stirred using a magnetic stirrer for 15 hours. The remaining amino groups were confirmed to be less than 1% by neutralization titration. Then, the reaction solution was transferred to a 200-mL four-necked flask equipped with a stirrer, a thermometer, and a condenser. To the solution were added 50 g of chlorobenzene and 50 g of water, and phase separation was performed. The organic phase was condensed to give 9.3 g of a transparent liquid (adhesion-imparting agent B).

(7) Measurement of the adhesion-imparting agent B by .sup.1H-NMR confirmed that the adhesion-imparting agent B included a structural unit represented by the formula (1-1) (R.sup.1a is methyl, A is methyl), a structural unit represented by the formula (1-2) (R.sup.1a is methyl, A is methyl), a structural unit represented by the formula (1-3) (R.sup.1b is methyl, A is a group represented by the formula (2), R.sup.2a is n-propylene, x is 0, R.sup.3 is methylene, R.sup.4 is hydroxymethyl), and a structural unit represented by the formula (1-4) (R.sup.1b is methyl).

(8) The refractive index of the adhesion-imparting agent B was measured to be 1.407 in the same manner as that for the adhesion-imparting agent A.

Production Example 3

Reaction of Silicone Compound Containing Phenyl and Amino Groups with Ethylene Carbonate (Preparation of Adhesion-Imparting Agent E)

(9) A 50-mL four-necked flask equipped with a magnetic stir bar, a thermometer, and a condenser was charged under a nitrogen atmosphere with 5.0 g (amino group 2.27 mmol) of a silicone compound containing phenyl and amino groups (“X-22-1660B-3” produced by Shin-Etsu Chemical Co., Ltd., amino group equivalent 2,200 g/mol) and 1.0 g (11.4 mmol) of ethylene carbonate (molecular weight 88.06). The contents were heated to 120° C. and stirred for 15 hours using a magnetic stirrer. The remaining amino groups were confirmed to be less than 1% by neutralization titration. Then, the reaction solution was transferred to a 200-mL four-necked flask equipped with a stirrer, a thermometer, and a condenser. To the solution were added 50 g of chlorobenzene and 50 g of water, and phase separation was performed. The organic phase was condensed to give 4.1 g of a transparent liquid (adhesion-imparting agent E).

(10) Measurement of the adhesion-imparting agent E by .sup.1H-NMR confirmed that the adhesion-imparting agent E included a structural unit represented by the formula (1-1) (R.sup.1a is methyl, A is a group represented by the formula (2), R.sup.2a is n-propylene, x is 0, R.sup.3 is methylene, R.sup.4 is hydrogen), a structural unit represented by the formula (1-2) (R.sup.1a is methyl, A is a group represented by the formula (2), R.sup.2a is n-propylene, x is 0, R.sup.3 is methylene, R.sup.4 is hydrogen), and a structural unit represented by the formula (1-4) (R.sup.1b is methyl or phenyl). The refractive index of the adhesion-imparting agent E was measured to be 1.502 using a digital Abbe refractometer (produced by ATAGO CO., LTD.) under the conditions of 25° C. and a wavelength of 589 nm.

Examples 1 to 7, Comparative Examples 1 to 5

(11) Ingredients in the amounts shown in Table 1 were uniformly mixed, and deaeration was sufficiently performed to prepare addition-curable silicone resin compositions.

(12) As the addition-curable silicone resin mixture A-1 in Table 1, a 1:1 mixture of a type A liquid and a type B liquid of OE-6370M (produced by Dow Corning Toray Co., Ltd.) was used. OE-6370M was an addition-curable silicone resin mixture with a refractive index of 1.409. The addition-curable silicone resin mixture A-1 contained a carbon-carbon double bond-containing polyorganosiloxane component and a polyorganohydrogensiloxane component.

(13) As the addition-curable silicone resin mixture B-1 in Table 1, a 1:1 mixture of a type A liquid and a type B liquid of KER-6150 (produced by Shin-Etsu Chemical Co., Ltd.) was used. KER-6150 was an addition-curable silicone resin mixture with a refractive index of 1.441. The addition-curable silicone resin mixture B-1 contained a carbon-carbon double bond-containing polyorganosiloxane component and a polyorganohydrogensiloxane component.

(14) As the adhesion-imparting agent C in Table 1, glycidoxypropyltrimethoxysilane (“Z-6040” produced by Dow Corning Toray Co., Ltd., refractive index 1.427) was used, and as the adhesion-imparting agent D, triglycidyl isocyanurate (produced by Tokyo Chemical Industry Co., Ltd., refractive index was not measurable due to its solid state) was used.

(15) <Evaluation>

(16) The addition-curable silicone resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were evaluated as follows. Table 1 shows the results.

(17) (1) Hardness (Type A)

(18) Each of the addition-curable silicone resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 was poured into a resin mold, and cured by heating at 150° C. for two hours, followed by heating at 170° C. for two hours. The resulting cured product was released from the mold, and formed into a test piece for hardness measurement with a radius of 20 mm and a thickness of 6 mm. The resulting test piece for hardness measurement was measured for hardness (Type A) using a hardness tester for rubber and plastics (“KR-24A” produced by KORI SEIKI MFG. CO., LTD.).

(19) (2) Tensile-Shear Adhesion Strength and Interfacial Adhesion to PCT

(20) Each of the addition-curable silicone resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 was poured between two PCT plates (“PROVEST C101LW” produced by Mitsui Chemicals, Inc., size 2×25×100 mm) so that the composition had a thickness of 2 mm and the plates were bonded at a 20×25 mm rectangular area. The composition was cured by heating at 150° C. for two hours, followed by heating at 170° C. for two hours. Thus, a test piece for a tensile-shear test was prepared. The PCT plates used as base materials for adhesion were dried at 150° C. for one hour before use. The obtained test piece was subjected to a tensile-shear adhesion test using a tensile tester (“AGS-X” produced by SHIMADZU CORPORATION) under the conditions of a distance between the clamps of 100 mm and a test speed of 5 mm/min. Thus, the tensile-shear adhesion strength was determined.

(21) The cross section was visually observed after the tensile-shear adhesion test to evaluate the interfacial adhesion. The failure patterns as shown in FIGS. 1A and 1B were represented by AF and the failure pattern as shown in FIG. 1C was represented by CF.

(22) (3) Tensile-Shear Adhesion Strength and Interfacial Adhesion to Silver-Plated Copper Plate

(23) Each of the addition-curable silicone resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 was poured between two silver-plated copper plates (size 2×25×100 mm) so that the composition had a thickness of 2 mm and the plates were bonded at a 20×25 mm rectangular area. The composition was cured by heating at 150° C. for two hours, followed by heating at 170° C. for two hours. Thus, a test piece for a tensile-shear test was prepared. The silver-plated copper plates used as base materials were dried at 150° C. for one hour before use. The test piece obtained was subjected to a tensile-shear adhesion test using a tensile tester (“AGS-X” produced by SHIMADZU CORPORATION) under the conditions of a distance between the clamps of 100 mm and a test speed of 5 mm/min. Thus, the tensile-shear adhesion strength was determined.

(24) The cross section was visually observed after the tensile-shear adhesion test to evaluate the interfacial adhesion. The failure patterns as shown in FIGS. 1A and 1B were represented by AF and the failure pattern as shown in FIG. 1C was represented by CF.

(25) (4) Total Light Transmittance

(26) Each of the addition-curable silicone resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 5 was poured on a PFA (tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer) plate so that the composition had a thickness of 1 mm. The composition was cured by heating at 150° C. for two hours, followed by heating at 170° C. for two hours. Thus, a test piece for a total light transmittance test was prepared. The resulting test piece for a total light transmittance test was measured for total light transmittance using a haze meter (“NDH 2000” produced by NIPPON DENSHOKU INDUSTRIES CO., LTD.).

(27) TABLE-US-00001 TABLE 1 Example Comparative Example 1 2 3 4 5 6 7 1 2 3 4 5 Composition Addition-curable silicone resin mixture A-1 100 100 100 100 100 100 — 100 100 100 — — (part by (“OE-6370M” produced by Dow Corning Toray mass) Co., Ltd. (refractive index 1.409)) Addition-curable silicone resin mixture B-1 — — — — — — 100 — — — 100 100 (“KER-6150” produced by Shin-Etsu Chemical Co., Ltd. (refractive index 1.441)) Adhesion- Adhesion- Adhesion- 0.5 1 3 — — — 1 — — — — — imparting imparting imparting agent agent agent A (refractive according index 1.407) to the Adhesion- — — — 0.5 1 3 — — — — — — present imparting agent invention B (refractive index 1.407) Other Adhesion- — — — — — — — — 1 — — — adhesion- imparting agent imparting C(refractive agents index 1.427) Adhesion- — — — — — — — — — 1 — — imparting agent D (no data of refractive index) Adhesion- — — — — — — — — — — — 1 imparting agent E (refractive index 1.502) Evaluation Hardness (Type A) 71 71 71 71 71 71 50 71 71 71 50 50 Tensile-shear Tensile-shear adhesion 1.3 1.6 1.7 1.4 1.7 1.9 1.2 0.8 1.0 1.1 0.5 1.0 adhesion strength (MPa) test for PCT Interface adhesion CF CF CF CF CF CF CF AF AF AF AF CF (failure pattern) Tensile-shear Tensile-shear adhesion 0.9 1.2 1.3 1.2 1.4 1.5 0.8 0.4 0.8 0.8 0.3 0.8 adhesion test strength (MPa) for silver-plated Interface adhesion CF CF CF CF CF CF CF AF AF AF AF CF copper plate (failure pattern) Total light transmittance (%) 92 92 92 92 92 92 93 92 92 86 93 85

Examples 8 to 14, Comparative Examples 6 to 10

(28) Ingredients in the amounts disclosed in Table 2 were uniformly mixed, and deaeration was sufficiently performed to prepare addition-curable silicone resin compositions.

(29) As the addition-curable silicone resin mixture A-2 in Table 2, a type A liquid of OE-6370M (produced by Dow Corning Toray Co., Ltd.) was used. The silicone resin mixture A-2 contained a carbon-carbon double bond-containing polyorganosiloxane component.

(30) As the addition-curable silicone resin mixture B-2 in Table 2, a type A liquid of KER-6150 (produced by Shin-Etsu Chemical Co., Ltd.) was used. The silicone resin mixture B-2 contained a carbon-carbon double bond-containing polyorganosiloxane component.

(31) As the adhesion-imparting agent C in Table 2, glycidoxypropyltrimethoxysilane (“Z-6040” produced by Dow Corning Toray Co., Ltd., refractive index 1.427) was used, and as the adhesion-imparting agent D in Table 2, triglycidyl isocyanurate (produced by Tokyo Chemical Industry Co., Ltd., refractive index could not be measured due to its solid state) was used.

(32) <Evaluation>

(33) The addition-curable silicone resin compositions obtained in Examples 8 to 14 and Comparative Examples 6 to 10 were evaluated as follows. Table 2 shows the results.

(34) (5) Storage Stability

(35) Each of the addition-curable silicone resin compositions obtained in Examples 8 to 14 and Comparative Examples 6 to 10 was kept warm at 70° C. for 30 days, and the initial viscosity (23° C.) and transmittance (wavelength 400 nm) of the composition before being kept warm were compared to the viscosity (23° C.) and transmittance (wavelength 400 nm) of the composition after being kept warm, respectively. The storage stability was evaluated from the amounts of changes of the viscosity and transmittance. The viscosities were measured using a digital viscometer DVH-EII (produced by Tokimec, Inc.), and the transmittances were measured using a U-4100 type spectrophotometer (produced by Hitachi High-Technologies Corporation.).

(36) TABLE-US-00002 TABLE 2 Example Comparative Example 8 9 10 11 12 13 14 6 7 8 9 10 Composition Addition-curable silicone resin mixture A-2 100 100 100 100 100 100 — 100 100 100 — — (part by (“OE-6370M” produced by mass) Dow Corning Toray Co., Ltd.) Addition-curable silicone resin mixture B-2 — — — — — — 100 — — — 100 100 (“KER-6150” produced by Shin-Etsu Chemical Co., Ltd.) Adhesion- Adhesion- Adhesion- 0.5 1 3 — — — 1 — — — — — imparting imparting imparting agent agent agent A (refractive according index 1.407) to the Adhesion- — — — 0.5 1 3 — — — — — — present imparting agent invention B (refractive index 1.407) Other Adhesion- — — — — — — — — 1 — — — adhesion- imparting agent imparting C (refractive agents index 1.427) Adhesion- — — — — — — — — — 1 — — imparting agent D (no data of refractive index) Adhesion- — — — — — — — — — — — 1 imparting agent E (refractive index 1.502) Evaluation Storage Amount of change of Less Less Less Less Less Less Less Less 1.2 Less Less Less stability viscosity (Pa .Math. s) than than than than than than than than than than than 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Amount of change of Less Less Less Less Less Less Less Less 2.2 Less Less Less transmittance (%) than than than than than than than than than than than 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

INDUSTRIAL APPLICABILITY

(37) The present invention can provide an addition-curable silicone resin composition with excellent interfacial adhesion properties, storage stability, and transparency. Furthermore, the present invention can provide an addition-curable silicone resin cured product formed from the addition-curable silicone resin composition and a sealed optical semiconductor element formed by using the addition-curable silicone resin composition.

REFERENCE SIGNS LIST

(38) 1 Adherend 2 Addition-curable silicone resin cured product