Silicone adhesive composition and solid-state imaging device

Abstract

The purpose of the present invention is to provide an adhesive composition using a silicone polymer compound, which does not require exposure, baking and development processes for the production, thereby making the production cost low and making the productivity high, which has good characteristics such as good adhesiveness, good hermetic sealing properties after thermal curing and low moisture absorption that are required for adhesives, which provides a cured film having high reliabilities such as high heat resistance and high light resistance, and which is capable of suppressing warping of a bonded substrate after back grinding that is necessary in the three-dimensional mounting production. A silicone adhesive composition which contains: (A) an organopolysiloxane containing a non-aromatic saturated monovalent hydrocarbon group and an alkenyl group; (B) an organohydrogenpolysiloxane containing two or more SiH groups in each molecule in such an amount that the molar ratio of the SiH groups in the component (B) is 0.5-10 relative to the alkenyl groups in the component (A); and (C) an effective amount of a platinum-based catalyst.

Claims

1. A silicone adhesive composition comprising (A) an organopolysiloxane containing a non-aromatic saturated monovalent hydrocarbon group and an alkenyl group, wherein said organopolysiloxane (A) is (A-1) an organopolysiloxane comprising the following units (I) to (III) and having a weight average molecular weight of 2,000 to 60,000, or (A-2) an organopolysiloxane having a weight average molecular weight of 20,000 to 400,000, obtained from hydrosilylation reaction of the organopolysiloxane (A-1) with at least one organohydrogenpolysiloxane having the general formula (1) in such amounts that a molar ratio of total SiH groups in the organohydrogenpolysiloxane to total alkenyl groups in the organopolysiloxane (A-1) may be in a range of 0.4/1 to 0.8/1, to achieve a molecular weight buildup, (I) 50 to 99 mol % of siloxane units (T units) of the formula: R.sup.1SiO.sub.3/2, (II) 0 to 49 mol % of siloxane units (D units) of the formula: R.sup.2R.sup.3SiO.sub.2/2, and (III) 1 to 15 mol % of siloxane units (M units) of the formula: R.sup.4.sub.3SiO.sub.1/2, wherein R.sup.1 to R.sup.3 each are a monovalent organic group, 2 to 10 mol % of the overall organic groups represented by R.sup.1 to R.sup.3 are alkenyl groups of 2 to 7 carbon atoms, at least 40 mol % of the overall organic groups represented by R.sup.1 to R.sup.3, which may be the same or different, are non-aromatic saturated monovalent hydrocarbon groups of 5 to 10 carbon atoms containing any one of the following cyclic structures: ##STR00010## and 10 to 40 mol % of the overall organic groups represented by R.sup.1 to R.sup.3, which may be the same or different, are substituted or unsubstituted, acyclic saturated monovalent hydrocarbon groups of 6 to 15 carbon atoms, and the balance being organic groups other than the alkenyl groups, the non-aromatic saturated monovalent hydrocarbon groups of 5 to 10 carbon atoms, and the acyclic saturated monovalent hydrocarbon groups of 6 to 15 carbon atoms, and R.sup.4 may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 7 carbon atoms, ##STR00011## wherein R.sup.5 to R.sup.7 may be the same or different and are monovalent hydrocarbon groups of 1 to 12 carbon atoms, exclusive of alkenyl, and n is an integer of 0 to 200; (B) an organohydrogenpolysiloxane containing at least two SiH groups per molecule in such an amount that a molar ratio of Sill groups in component (B) to alkenyl groups in component (A) may be in a range of 0.5/1 to 10/1; (C) an effective amount of a platinum-based catalyst; and (D) a reaction inhibitor.

2. The adhesive composition of claim 1, further comprising (E) an antioxidant.

3. The adhesive composition of claim 1, further comprising (F) an organic solvent.

4. The adhesive composition of claim 3 wherein the organic solvent (F) is a hydrocarbon solvent having a boiling point of 120 to 240° C.

5. A silicone adhesive composition comprising (A) an organopolysiloxane containing a non-aromatic saturated monovalent hydrocarbon group and an alkenyl group, wherein said organopolysiloxane (A) is (A-1) an organopolysiloxane comprising the following units (I) to (III) and having a weight average molecular weight of 2,000 to 60,000, or (A-2) an organopolysiloxane having a weight average molecular weight of 20,000 to 400,000, obtained from hydrosilylation reaction of the organopolysiloxane (A-1) with at least one organohydrogenpolysiloxane having the general formula (1) in such amounts that a molar ratio of total SiH groups in the organohydrogenpolysiloxane to total alkenyl groups in the organopolysiloxane (A-1) may be in a range of 0.4/1 to 0.8/1, to achieve a molecular weight buildup, (I) 50 to 99 mol % of siloxane units (T units) of the formula: R.sup.1SiO.sub.3/2, (II) 0 to 49 mol % of siloxane units (D units) of the formula: R.sup.2R.sup.3SiO.sub.2/2, and (III) 1 to 15 mol % of siloxane units (M units) of the formula: R.sup.4.sub.3SiO.sub.1/2, wherein R.sup.1 to R.sup.3 each are a monovalent organic group, 2 to 10 mol % of the overall organic groups represented by R.sup.1 to R.sup.3 are alkenyl groups of 2 to 7 carbon atoms, at least 40 mol % of the overall organic groups represented by R.sup.1 to R.sup.3, which may be the same or different, are non-aromatic saturated monovalent hydrocarbon groups of 5 to 10 carbon atoms containing any one of the following cyclic structures: ##STR00012## and 10 to 40 mol % of the overall organic groups represented by R.sup.1 to R.sup.3, which may be the same or different, are substituted or unsubstituted, acyclic saturated monovalent hydrocarbon groups of 6 to 15 carbon atoms, and the balance being organic groups other than the alkenyl groups, the non-aromatic saturated monovalent hydrocarbon groups of 5 to 10 carbon atoms, and the acyclic saturated monovalent hydrocarbon groups of 6 to 15 carbon atoms, and R.sup.4 may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 7 carbon atoms ##STR00013## wherein R.sup.5 to R.sup.7 may be the same or different and are monovalent hydrocarbon groups of 1 to 12 carbon atoms, exclusive of alkenyl, and n is an integer of 0 to 200; (B) an organohydrogenpolysiloxane containing at least two SiH groups per molecule in such an amount that a molar ratio of SiH groups in component (B) to alkenyl groups in component (A) may be in a range of 0.5/1 to 10/1; and (C) an effective amount of a platinum-based catalyst, which adhesive composition is sandwiched between a protective glass substrate and a substrate which is selected from the group consisting of a silicon wafer, solid-state imaging device silicon wafer, plastic substrate, ceramic substrate, and metallic circuit substrate.

6. A solid-state imaging device comprising a laminate including a substrate which is selected from the group consisting of a silicon wafer, solid-state imaging device silicon wafer, plastic substrate, ceramic substrate, and metallic circuit substrate, on which a cured layer of a silicone adhesive composition comprising (A) an organopolysiloxane containing a non-aromatic saturated monovalent hydrocarbon group and an alkenyl group, wherein said organopolysiloxane (A) is (A-1) an organopolysiloxane comprising the following units (I) to (III) and having a weight average molecular weight of 2,000 to 60,000, or (A-2) an organopolysiloxane having a weight average molecular weight of 20,000 to 400,000, obtained from hydrosilylation reaction of the organopolysiloxane (A-1) with at least one organohydrogenpolysiloxane having the general formula (1) in such amounts that a molar ratio of total SiH groups in the organohydrogenpolysiloxane to total alkenyl groups in the organopolysiloxane (A-1) may be in a range of 0.4/1 to 0.8/1, to achieve a molecular weight buildup, (I) 50 to 99 mol % of siloxane units (T units) of the formula: R.sup.1SiO.sub.3/2, (II) 0 to 49 mol % of siloxane units (D units) of the formula: R.sup.2R.sup.3SiO.sub.2/2, and (III) 1 to 15 mol % of siloxane units (M units) of the formula: R.sup.4.sub.3SiO.sub.1/2, wherein R.sup.1 to R.sup.3 each are a monovalent organic group, 2 to 10 mol % of the overall organic groups represented by R.sup.1 to R.sup.3 are alkenyl groups of 2 to 7 carbon atoms, at least 40 mol % of the overall organic groups represented by R.sup.1 to R.sup.3, which may be the same or different, are non-aromatic saturated monovalent hydrocarbon groups of 5 to 10 carbon atoms containing any one of the following cyclic structures: ##STR00014## and 10 to 40 mol % of the overall organic groups represented by R.sup.1 to R.sup.3, which may be the same or different, are substituted or unsubstituted, acyclic saturated monovalent hydrocarbon groups of 6 to 15 carbon atoms, and the balance being organic groups other than the alkenyl groups, the non-aromatic saturated monovalent hydrocarbon groups of 5 to 10 carbon atoms, and the acyclic saturated monovalent hydrocarbon groups of 6 to 15 carbon atoms, and R.sup.4 may be the same or different and is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 7 carbon atoms ##STR00015## wherein R.sup.5 to R.sup.7 may be the same or different and are monovalent hydrocarbon groups of 1 to 12 carbon atoms, exclusive of alkenyl, and n is an integer of 0 to 200; (B) an organohydrogenpolysiloxane containing at least two SiH groups per molecule in such an amount that a molar ratio of SiH groups in component (B) to alkenyl groups in component (A) may be in a range of 0.5/1 to 10/1; (C) an effective amount of a platinum-based catalyst and a protective glass substrate are stacked in order.

Description

EXAMPLES

(1) Synthesis Examples, Comparative Synthesis Examples, Examples, Comparative Examples are given below for further illustrating the invention although the invention is not limited thereto. It is noted that in Examples, Me stands for methyl, the viscosity is a measurement at 25° C. by a rotational viscometer, and the weight average molecular weight is a value determined by GPC versus polystyrene standards.

Synthesis of Organopolysiloxanes

Synthesis Example 1

(2) A 1-L flask equipped with a stirrer, condenser and thermometer was charged with 234 g (13 moles) of water and 35 g of toluene and heated at 80° C. in an oil bath. A dropping funnel was charged with 108.8 g (0.5 mole) of cyclohexyltrichlorosilane, 65.9 g (0.3 mole) of n-hexyltrichlorosilane, 6.5 g (0.05 mole) of dimethyldichlorosilane, 7.1 g (0.05 mole) of methylvinyldichlorosilane, and 10.9 g (0.1 mole) of trimethylchlorosilane, which was added dropwise to the flask over 1 hour while stirring. After the completion of dropwise addition, stirring was continued at 80° C. for 1 hour for ripening. The solution was cooled to room temperature while it was kept static. The separated water phase was removed. Subsequently, the procedure of combining the toluene phase with 10 wt % sodium sulfate aqueous solution, stirring for 10 minutes, keeping static for 30 minutes, and removing the separated water phase was repeated until the toluene phase became neutral, whereby the reaction was stopped. After the flask was equipped with an ester adaptor, the organopolysiloxane-containing toluene phase was heated under reflux to remove water from the toluene phase. After the internal temperature reached 110° C., heating under reflux was continued for a further 1 hour. The solution was cooled to room temperature. The resulting organopolysiloxane solution was filtered to remove the insoluble matter. Subsequent distillation under reduced pressure to remove toluene yielded 115.2 g of an organopolysiloxane (A-I) in solid form.

(3) The resulting organopolysiloxane (A-I) consisted of 80 mol % of T units, 10 mol % of D units, and 10 mol % of M units, and contained at ends 0.09 mole of silanol groups and 0.043 mole of vinyl groups per 100 g of organopolysiloxane (A-I). It looked to be a colorless transparent solid and had a weight average molecular weight of 7,500. It had a cyclohexyl content of 38 mol %, a n-hexyl content of 23 mol %, and a vinyl content of 3.8 mol % based on the overall organic groups. Cyclohexyl, n-hexyl, methyl, and vinyl groups accounted for 50 mol %, 30 mol %, 15 mol %, and 5 mol % of the overall organic groups represented by R.sup.1 to R.sup.3, respectively.

Synthesis Example 2-1

(4) Synthesis was carried out as in Synthesis Example 1 except that a 2-L flask was charged with 468 g (26 moles) of water and 70 g of toluene and heated at 80° C. in an oil bath, and a dropping funnel was charged with 275.6 g (1.2 moles) of norbornyltrichlorosilane, 65.8 g (0.3 mole) of n-hexyltrichlorosilane, 25.8 g (0.2 mole) of dimethyldichlorosilane, 14.2 g (0.1 mole) of methylvinyldichlorosilane, and 21.8 g (0.2 mole) of trimethylchlorosilane. There was obtained 228.8 g of an organopolysiloxane in solid form.

(5) The resulting organopolysiloxane consisted of 75 mol % of T units, 15 mol % of D units, and 10 mol % of M units, and contained 0.07 mole of silanol groups and 0.039 mole of vinyl groups per 100 g. It looked to be a colorless transparent solid and had a weight average molecular weight of 9,300. It had a norbornyl content of 44 mol %, a n-hexyl content of 11 mol %, and a vinyl content of 3.7 mol % based on the overall organic groups. Norbornyl, n-hexyl, methyl and vinyl groups accounted for 57 mol %, 14 mol %, 24 mol %, and 5 mol % of the overall organic groups represented by R.sup.1 to R.sup.3, respectively.

Synthesis Example 2-2

(6) The solid organopolysiloxane obtained in Synthesis Example 2-1, 100 g, was dissolved as the alkenyl-containing organopolysiloxane in 100 g of toluene to form a solution having a solid concentration of 50 wt %. To this solution, a platinum-based catalyst was added to provide 20 ppm of platinum atom based on the resin. After the solution was heated at 60° C., 44.6 g of a compound (SiH equivalent 2,287 g/mol) having the formula (4) shown below, which amount corresponded to a H/Vi ratio (a ratio of SIR groups to total alkenyl groups) of 0.5, as the hydrosilyl-containing compound was added dropwise, during which an exotherm due to reaction was observed. Reaction was continued at 100° C. for 2 hours to completion. By carrying out distillation under reduced pressure for concentrating and distilling off toluene, the reaction product was solidified, obtaining an organopolysiloxane (A-II). The resin had a weight average molecular weight (Mw) of 41,000 as measured by GPC and contained 0.019 mol of vinyl groups per 100 g.

(7) ##STR00007##

Synthesis Example 3-1

(8) Synthesis was carried out as in Synthesis Example 1 except that a 1-L flask was charged with 234 g (13 moles) of water and 35 g of toluene and heated at 80° C. in an oil bath, and a dropping funnel was charged with 160.7 g (0.7 mole) of norbornyltrichlorosilane, 45.6 g (0.15 mole) of n-dodecyltrichlorosilane, 7.1 g (0.05 mole) of methylvinyldichlorosilane, and 10.9 g (0.1 mole) of trimethylchlorosilane. There was obtained 143.8 g of an organopolysiloxane in solid form.

(9) The resulting organopolysiloxane consisted of 85 mol % of T units, 5 mol % of D units, and 10 mol % of M units, and contained 0.1 mole of silanol groups and 0.034 mole of vinyl groups per 100 g. It looked to be a colorless transparent solid and had a weight average molecular weight of 6,100. It had a norbornyl content of 56 mol %, a n-dodecyl content of 12 mol %, and a vinyl content of 4.0 mol % based on the overall organic groups. Norbornyl, n-dodecyl, methyl and vinyl groups accounted for 74 mol %, 16 mol %, 5 mol %, and 5 mol % of the overall organic groups represented by R′ to R.sup.3, respectively.

Synthesis Example 3-2

(10) Reaction was conducted as in Synthesis Example 2-2 except that 100 g of the solid organopolysiloxane obtained in Synthesis Example 3-1 was used as the alkenyl-containing organopolysiloxane, and 31.6 g of a compound (SiH equivalent 1,547 g/mol) having the formula (5) shown below, which amount corresponded to a H/Vi ratio of 0.6, was used as the hydrosilyl-containing compound. There was obtained an organopolysiloxane (A-III) having a weight average molecular weight of 46,400. The resin contained 0.02 mol of vinyl groups per 100 g.

(11) ##STR00008##

Comparative Synthesis Example 1

(12) Synthesis was carried out as in Synthesis Example 1 except that a 1-L flask was charged with 234 g (13 moles) of water and 35 g of toluene and heated at 80° C. in an oil bath, and a dropping funnel was charged with 137.5 g (0.65 mole) of phenyltrichlorosilane, 50.6 g (0.2 mole) of diphenyldichlorosilane, 7.1 g (0.05 mole) of methylvinyldichlorosilane, and 10.8 g (0.1 mole) of trimethylchlorosilane. There was obtained 137 g of an organopolysiloxane (A-IV) in solid form.

(13) The resulting organopolysiloxane (A-IV) consisted of 65 mol % of T units, 25 mol % of D units, and 10 mol % of M units, and contained at ends 0.01 mole of silanol groups and 0.034 mole of vinyl groups per 100 g of the organopolysiloxane. It looked to be a colorless transparent solid and had a weight average molecular weight of 11,700. Phenyl (aromatic unsaturated hydrocarbon), methyl, and vinyl groups accounted for 92 mol %, 4 mol %, and 4 mol % of the overall organic groups represented by R.sup.1 to R.sup.3, respectively.

Comparative Synthesis Example 2

(14) Synthesis was carried out as in Synthesis Example 1 except that a 1-L flask was charged with 234 g (13 moles) of water and 35 g of toluene and heated at 80° C. in an oil bath, and a dropping funnel was charged with 91.8 g (0.4 mole) of norbornyltrichlorosilane, 24.7 g (0.15 mole) of n-hexyltrichlorosilane, 45.2 g (0.35 mole) of dimethyldichlorosilane, 7.1 g (0.05 mole) of methylvinyldichlorosilane, and 5.4 g (0.05 mole) of trimethylchlorosilane. There was obtained 143.8 g of an organopolysiloxane (A-V) in solid form.

(15) The resulting organopolysiloxane consisted of 55 mol % of T units, 40 mol % of D units, and 5 mol % of M units, and contained 0.12 mole of silanol groups and 0.044 mole of vinyl groups per 100 g. It looked to be a colorless transparent solid and had a weight average molecular weight of 10,500. It had a norbornyl content of 27 mol %, a n-hexyl content of 10 mol %, and a vinyl content of 3.3 mol % based on the overall organic groups. Norbornyl, n-hexyl, methyl, and vinyl groups accounted for 30 mol %, 11 mol %, 55 mol %, and 4 mol % of the overall organic groups represented by R.sup.1 to R.sup.3, respectively.

Examples 1 to 3 & Comparative Examples 1, 2

(16) The above organopolysiloxane A-I, A-II or A-III or comparative organopolysiloxane A-IV or A-V was used as component (A), and components (B), (C), (D), (E) and (F) were added according to the formulation shown in Table 1, followed by stirring, mixing and dissolution. The following compound (B-I) or (B-II) was used as component (B).

(17) ##STR00009##

(18) There were also used a platinum catalyst CAT-PL-50T (Shin-Etsu Chemical Co., Ltd.) as component (C), ethynyl cyclohexanol as component (D), a phenol based antioxidant Adeka Stab AO-60 as component (E), and isononane as component (F). The compositions were precision filtered through a Teflon® filter having a size of 0.2 μm, obtaining inventive adhesive compositions of Examples 1 to 3 and adhesive compositions of Comparative Examples 1 and 2.

(19) Using a spin coater, each of the adhesive compositions of Examples 1 to 3 and Comparative Examples 1 and 2 in Table 1 was coated on a 8-inch silicon wafer to the thickness shown in Table 1. The coating was prebaked on a hot plate at 80° C. for 5 minutes to remove the solvent. Using a bonding machine, the 8-inch silicon wafer coated with the adhesive composition was temporarily bonded under conditions including a bonding temperature of 100° C., a holding time (prior to bonding) of 1 minute, a reduced pressure (during bonding) of 4×10.sup.3 mbar, and a bonding pressure of 2 kN. The temporary bonded substrate was heat cured at 150° C. for 5 minutes, yielding a final bonded substrate.

(20) Various tests were carried out by the following methods.

(21) [Adhesion Test]

(22) Bonding of a 8-inch wafer was carried out using a wafer bonding system 520IS of EVG. After bonding and cooling to room temperature, the bonded interface was visually observed. The rating is good (◯) when no anomalies are detected at the interface or poor (x) when anomalies like bubbles are detected.

(23) [Back Grinding Resistance Test]

(24) Using a grinder DAG810 of Disco Corp., the back surface of the silicon substrate was ground. After grinding to a final thickness of 50 μm, the substrate was observed under an optical microscope to inspect anomalies such as cracks and peels. The rating is good (◯) when no anomalies are detected or poor (x) when anomalies are detected.

(25) [Heat Resistance]

(26) The bonded assembly after back grinding of the silicon substrate was heated on a hot plate at 230° C. or 260° C. for 3 minutes in air, before the outer appearance was inspected for anomalies. The rating is good (◯) when no appearance anomalies are detected or poor (x) when appearance anomalies or peels are detected.

(27) [Light Resistance]

(28) For examining light resistance, the following short-term and long-term light resistance tests were carried out.

(29) In the short-term light resistance test, the adhesive composition was spin coated on a glass substrate to a film thickness of 500 μm, and heat cured at 150° C. for 10 minutes, whereupon an initial transmittance (wavelength 400 nm) was measured. Next, it was heated on a hot plate at 230° C. or 260° C. for 3 minutes in air, whereupon a transmittance (wavelength 400 nm) after heating was measured again. A percent attenuation was computed as [(transmittance @400 nm after heating)/(initial transmittance @400 nm)]×100. The rating is good (◯) for an attenuation of at least 90% or poor (x) for an attenuation of less than 90%.

(30) In the long-term light resistance test, the adhesive composition was spin coated on a glass substrate to a film thickness of 500 μm, and heat cured at 150° C. for 10 minutes, whereupon an initial transmittance (wavelength 400 nm) was measured. Next, it was exposed to simulative sunlight (with wavelength 350 nm and shorter cut off) at 5,000,000 lux, whereupon a transmittance (wavelength 400 nm) after light exposure was measured again. A percent attenuation was computed as [(transmittance @400 nm after light exposure)/(initial transmittance @400 nm)]×100. The rating is good (◯) for an attenuation of at least 90% or poor (x) for an attenuation of less than 90%.

(31) [Warpage (Warpage of Bonded Wafer)]

(32) Using a back polishing machine, an assembly obtained by bonding and heat curing a 8-inch silicon wafer substrate and a protective glass substrate using the adhesive composition was polished on the silicon side from an initial thickness of 725 μm to a thickness of 100 μm. After back polishing, the bonded 8-inch wafer was measured for warpage.

(33) The test results are shown in Table 1.

(34) TABLE-US-00001 TABLE 1 Comparative Comparative (pbw) Example 1 Example 2 Example 3 Example 1 Example 2 Component (A) A-I A-II A-III A-IV A-V (100) (100) (100) (100) (100) Component (B) B-I B-I B-II B-I B-II (15) (6.5) (9) (12) (20) Component (C) CAT-PL-50T CAT-PL-50T CAT-PL-50T CAT-PL-50T CAT-PL-50T (0.5) (0.5) (0.5) (0.5) (0.5) Component (D) ethynyl ethynyl ethynyl ethynyl ethynyl cyclo-hexanol cyclo-hexanol cyclo-hexanol cyclo-hexanol cyclo-hexanol (0.1) (0.1) (0.1) (0.1) (0.1) Component (E) Adeka Stab Adeka Stab Adeka Stab Adeka Stab Adeka Stab AO-60 AO-60 AO-60 AO-60 AO-60 (1) (1) (1) (1) (1) Component (F) isononane isononane isononane isononane isononane (45) (50) (50) (45) (45) molar ratio of 2.1 2.2 1.9 2.2 1.9 SiH groups in component (B) to alkenyl groups in component (A) Film thickness (μm) 30 30 30 30 30 Test Adhesion ∘ ∘ ∘ ∘ ∘ results Back grinding ∘ ∘ ∘ ∘ ∘ resistance Heat 230° C. ∘ ∘ ∘ ∘ ∘ resistance 260° C. ∘ ∘ ∘ ∘ x Short-term ∘ ∘ ∘ x ∘ light resistance Long-term ∘ ∘ ∘ x ∘ light resistance Warpage (μm) 11.3 8.9 7.7 51.1 5.2

(35) It is seen from Table 1 that on use of a norbornyl-free phenyl silicone resin as in Comparative Example 1, light resistance and warpage are exacerbated, and on use of a resin with a low norbornyl content as in Comparative Example 2, warpage is good, but heat resistance is degraded. In contrast, all Examples 1 to 3 are excellent in heat resistance, light resistance and warpage. That is, the adhesive composition of the invention meets the aforementioned requirements.

(36) It has been demonstrated that the silicone adhesive composition of the invention has advantages of low manufacture cost and high productivity because exposure, bake and development steps are unnecessary for the manufacture process, has satisfactory properties needed as adhesive including adhesion, hermetic seal after heat curing, and low hygroscopicity, and forms a cured film with high reliability in terms of heat resistance and light resistance, and can reduce the warpage of bonded substrate after back grinding as required in the 3D package manufacture.

(37) It is noted that the invention is not limited to the aforementioned embodiments. While the embodiments are merely exemplary, any embodiments having substantially the same construction as the technical concept set forth in the following claims and achieving equivalent functions and results are believed to be within the spirit and scope of the invention.